WO2018091448A1

WO2018091448A1 - Polyethers based on oxetanes for use as wetting agents and as dispersants and production thereof

Info

Publication number: WO2018091448A1
Application number: PCT/EP2017/079159
Authority: WO
Inventors: Michael Bessel; Guillaume Wojciech JAUNKY; Frederik Piestert; Carsten Nagel; Sandra Sabrina MEYER; Dennis LEVERING
Original assignee: Byk-Chemie Gmbh
Priority date: 2016-11-15
Filing date: 2017-11-14
Publication date: 2018-05-24

Abstract

The invention relates to polyethers of the following general formula (I), wherein the residues R¹, R², R³, R⁴, R^5a (as a special case of residue R⁵), R⁶, R⁷ and R⁸ are free of carboxy, hydroxy, thiol, imino, and primary and secondary amino groups, the residues R^5b (as a special case of R⁵) and R⁹ contain hydroxyl groups, which can be present in salt form analogously to polymers or otherwise capped, u = 0 or 1, v = 1 to 60 and w = 1 to 20, and at least one of the residues R², R³, R⁴, R⁵, R⁵, R⁶, R⁷ and R⁸ contains an aromatic or araliphatic residue. The invention further relates to wetting agents and dispersants that contain the aforementioned polyethers or consist thereof and to a method for producing said wetting agents and dispersants, to the use of the polyethers and reaction products of the method according to the invention as wetting agents and dispersants, and to compositions containing the polyethers, wetting agents and/or dispersants or reaction products of the method according to the invention and particulate solids.

Description

Polyethers based on oxetanes for use as network and

Dispersants and their preparation

The present invention relates to polyethers based on oxetanes which are suitable as wetting and / or dispersing agents, and to the preparation thereof, to their use as or in wetting agents and / or dispersants, and to the use of wetting and dispersing agents in various compositions.

Technological background of the invention

In order to distribute solids in a liquid or solid medium, such as, for example, in coatings, aqueous or organic solvent dispersions or polymer molding compositions, stably and homogeneously, wetting agents and / or dispersants are needed as auxiliaries. For this, they have to fulfill two different functions.

First, they must be able to interact with the solid surface to facilitate their wetting. This is achieved by the wetting and dispersing agents having certain chemical groups, so-called adhesive groups. Examples of hydrophilic adhesive groups are tertiary amino

Groups, protonated or quaternized amino groups, phosphoric acid groups, carboxylic acid groups, sulfonic acid groups or amide, urethane and / or urea groups. Hydrophobic groups such as alkyl radicals, phenyl or benzyl radicals, for example as described in Adv. Mater. 1998, 10, 1215-1218.

Second, wetting and dispersing agents must be well tolerated with the dispersing medium. For organic dispersing media, dispersants should therefore usually have hydrophobic radicals, such as, for example, relatively long-chain alkyl radicals or aryl radicals. For aqueous dispersing media, the dispersants water-soluble, hydrophilic radicals, such as, for example, salified carboxylic acids.

Polymerization of monomers gives polymeric dispersants, which can optionally be subsequently modified by a polymer-analogous reaction, for example in the side chains. Depending on how the polymerization is carried out, the monomers in the polymer chain are incorporated randomly or alternately, in a gradient-like or block-like manner. In a random or alternating structure of the polymer chains such dispersants usually show very good solids wetting properties, but in comparison to wetting and dispersing agents with a gradient-like or block-like structure, a poorer stabilization of the solid dispersion. In contrast, the block-like structure of dispersants having very good stabilizing properties can lead to micellization of the polymer chains in strongly differently polar blocks, which leads to a poorer wetting behavior of the solid surface of the solid to be dispersed.

A large group of wetting and dispersing agents is based on polymers of ethylenically unsaturated monomers such. As acrylates or methacrylates, wherein the polymers used can have both a statistical, gradient-like or block-like structure. If polymers or copolymers have a statistical structure, they are prepared by free-radical polymerization with the aid of customary starters. If they have a gradient-like or block-like structure, they are controlled by a controlled polymerization such. Atom Transfer Radical Polymerization (ATRP), Group Transfer Polymerization (GTP), Nitroxyl Mediated Polymerization (NMP) or a Reversible Addition Fragmentation Chain Transfer Process (RAFT). For the preparation of copolymers with a block-like or gradient-like structure according to controlled polymerization technologies, special and thus expensive initiators or catalysts are usually required. Wetting and dispersing agents based on such polymers are known to the person skilled in the art known in the relevant literature. However, because of the different chemical starting materials, these wetting and dispersing agents are not related to the polyethers of the present invention. Another important group of wetting and dispersing agents is based on polyalkylene oxides. By polymerization of ethylene oxide, these wetting and dispersing agents have a hydrophilic character, while by copolymerization of propylene, butylene or styrene oxide, hydrophobic groups can be incorporated into the polymer forming the wetting and dispersing agent. Since there is only a small selection of commercially available alkylene oxides and only terminal OH groups are suitable as functional group for modifications in these polymers, there is only a limited possibility for modifying the polymers and thus for their use as wetting and dispersing agents.

As a solution to the disadvantages of the abovementioned pure polyalkylene oxides, US Pat. No. 1/257326 A1 proposes oxetane-group-free polyglycidyl ether block copolymers as dispersants, which are obtained by means of anionic ring-opening polymerization.

JP 2005 068292 A discloses a process for the preparation of polyether monools or polyether polyols by ring-opening copolymerization of an oxetane and oxirane having more than 3 carbon atoms in the presence of an initiator having at least one hydroxyl group and a complex metal cyanide complex as a catalyst.

EP 2 468 835 A1 discloses cationically polymerizable adhesives comprising a polyether polyol, a compound containing oxetanyl groups, an aromatic glycidyl ether and a polymerization initiator for cationic polymerisation.

No. 6,124,402 A describes polyaddition copolymers which comprise structural units derived from bisphenol A and bisoxetanes. US 2006/041032 A1 discloses prepolymer mixtures comprising two catalyst components, the first containing a cationic photoinitiator and the second containing a free radical photoinitiator, and a monomer component selected from oxetane and epoxide monomers.

US 2007/144400 A1 discloses a cationic polymerizable resin composition comprising a compound having at least one functional group capable of cationic ring-opening polymerization, a cationic polymerization initiator capable of generating active species by electromagnetic waves or particle radiation, and a compound containing is capable of carbocation formation by the aforementioned active species.

US Pat. No. 3,499,759 A relates to a photosensitive copying material having a photocrosslinkable layer which contains or consists of crosslinkable polyethers, the layer being crosslinkable polyethers comprising at least one photosensitive polymer of an oxetane or a copolymer of such oxetane and a non-photosensitive, if appropriate substituted oxirane, oxetane, oxolane or tetrahydrofuran.

Despite the use of styrene oxide-alkylene oxide block copolymers and polyglycidyl ether block copolymers known from the prior art, there continues to be an urgent need for improved wetting and dispersing agents, especially improved compatibility of pigment concentrates prepared with these wetting and dispersing agents with different make-up binders , This is even more so if they are to be used for a variety of applications.

Structurally similar to the species of the present invention, compounds are disclosed in US 8,258,189 B2 for the cosmetics industry. However, the compounds described therein do not have any aromatic radicals which have been introduced into the target species via oxiranes or oxetanes in the present invention. be brought. Such compounds described in US Pat. No. 8,258,189 B2, however, give no useful results, particularly in the case of the preparation of pigmented pastes. The various fields of application include inter alia pigmented and / or fillers containing synthetic resins or molding compositions, which include the aforementioned SMC and BMC, which often and in particular consist of reinforcing fibers and fillers containing unsaturated polyester resins. Suitable wetting agents and dispersants based on phosphated oxetane group-free polyether polyesters which are suitable for this purpose, but whose effectiveness and compatibility can be improved, are known, for example, from US Pat. No. 5,130,463.

A structural similarity to the species of the present invention also have the species described in US 2013/0289195 A1, which necessarily have a terminal ethylenically unsaturated functional group such as an acrylate, methacrylate, vinyl or allyl group. Their effect is based, inter alia, on the direct attachment of the ethylenically unsaturated group to constituents of the dispersion medium. The object of the present invention was therefore to provide agents for the phase transfer between solid and liquid, that is to say wetting and / or dispersing agents which have storage stability in both hydrophobic and hydrophilic media with improved compatibility with different lacquer binders and lead with wide applications. Particularly noteworthy is also the task of finding wetting and dispersing agents which, even without the use of additional binders, are able to obtain homogeneous pigmented acridations which can then be used universally in various coating agent systems and have high color stability.

The above objects have been achieved by providing polyethers of the following general formula (I) or wetting and / or dispersing agents consisting of these or containing them:

(I)

wherein

u stands for 0 or 1

v is from 1 to 60, preferably from 2 to 45, more preferably from 6 to 40, w is from 1 to 20, preferably from 1 to 10, more preferably from 1 to 6, R ^{1 is} a monovalent organic radical having from 1 to 100, preferably from 1 to 80 and more preferably 1 to 50 carbon atoms,

R ^{2 is} a divalent organic radical, and the

when u = 0 is CHR ^2a CHR ^2b , where

R ^2a and R ^2b are each independently

Hydrogen, or

monovalent organic radicals selected from the group consisting of

aliphatic radicals having 1 to 8 carbon atoms, aromatic radicals having 6 to 8 carbon atoms, or araliphatic radicals having 7 to 10 carbon atoms; and the

when u = 1 is an aliphatic radical having 2 to 24 carbon atoms;

R ³ , R ⁴ , R ⁷ and R ⁸ are each independently

Hydrogen, or

monovalent organic radicals are and are selected from the group consisting of

aliphatic radicals having 1 to 8 carbon atoms,

aromatic radicals having 6 to 8 carbon atoms, or

araliphatic radicals having 7 to 10 carbon atoms,

R ^{5 is} a radical R ^5a or R ^5b , and R ^5a for

is a monovalent organic radical and is selected from the group consisting of

aliphatic radicals having 1 to 20 carbon atoms, aromatic radicals having 6 to 12 carbon atoms, araliphatic radicals having 7 to 24 carbon atoms,

R ^5b for

a radical CH 2 -OR ^5c , wherein R ^{5c is}

Hydrogen or

a monovalent one or more hydroxyl-containing organic radical and which is selected from the group consisting of

aliphatic radicals having 1 to 24 carbon atoms, aromatic radicals having 6 to 14 carbon atoms, and araliphatic radicals having 7 to 18 carbon atoms, R ^{6 is} hydrogen or a radical R ^5a

R ⁹ is defined as R ^5c and is independently selected from R ^5c ; and

in which

(a) the radicals R ¹ , R ² , R ³ , R ⁴ , R ^5a , R ⁶ , R ⁷ and R ^{8 are} free of carboxy,

hydroxy,

Thiol, imino, and primary and secondary amino groups,

(b) at least one, preferably 2 to 6, more preferably 2 to 4 of the radicals R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ contained in formula (I) are aromatic or araliphatic radicals or contain an aromatic or araliphatic radical, and

(C) 0 to 100 mol%, preferably 10% to 100 mol%, particularly preferably 20% or 30 to 100 mol% of the over the above radicals R ^5b and R ⁹ or by elimination of hydrolytically removable radicals by hydroxyl groups Residues OT are replaced, which are selected from the group consisting of Radicals -Ο-Ρ (Ο) (ΟΗ) ₂ -χ (Ο © Ζ ©) χ, where x is 0, 1 or 2,

Residues -OS (O2) (OH) i _-y (O © © Z) _y wherein y is 0 or 1, and

Residues -O- (C = O) _s - (NH) _t -T ^a wherein s is 0 or 1 and t is 0 or 1, and in the case that s = 0 and t = 0, and wherein T ^{a is} a monovalent organic radical having 1 to 100 carbon atoms, which optionally has one or more of the following radicals COOH,

-COO © Z®,

-OP (O) (OH) _2- x (O © Z ©) _x and

-OS (O ₂ ) (OH) i _-y (O © Z ©) _y , and the above radicals Z® independently of one another represent alkali metal cations, an ammonium ion or protonated or quaternized amines.

The term "organic radical" as used herein means an aliphatic, aromatic or araliphatic radical.

The term "aliphatic radical" as used herein means, in accordance with the IU-PAC nomenclature (for reference: "aliphatic compounds", Pure & Appl. Chem., 67 (8/9) (1995), 1307-1375, 1313) - That it is an acyclic or cyclic, saturated or unsaturated, non-aromatic radical of a carbon compound. The term "aliphatic radical" thus also includes the cycloaliphatic radicals (also referred to as alicyclic radicals). For the radicals for which carboxy groups (COOH groups) are not explicitly excluded, an aliphatic radical could in principle also be a carboxyl group, since it is the nonaromatic radical of a carbon compound, namely formic acid. An aliphatic radical usually also contains hydrogen atoms in addition to carbon atoms. In addition, an aliphatic radical may also contain heteroatoms, which in the latter case is a so-called heteroaliphatic radical. The term "aromatic radical" as used herein means, in accordance with the usual meaning, that it is the radical of a ring system of a carbon compound which, according to the Hückel rule in conjugated double bonds, lone-pair electrons or unoccupied p orbitals, has a number of 4n An aromatic radical usually contains not only carbon atoms but also hydrogen atoms In addition, an aromatic radical may also contain heteroatoms, in the latter case being a so-called heteroaromatic radical. Preferred heteroatoms are, for example, nitrogen atoms and / or oxygen atoms.

As used herein, the term "aliphatic radical" means an aliphatic radical substituted with one or more aromatic radicals.

The term "hydrocarbyl radical" as used herein in accordance with the IUPAC nomenclature refers to a radical containing only carbon atoms and hydrogen atoms, in those cases in which such radical may additionally contain one or more heteroatoms (for example ether oxygen atoms) or with one or a plurality of heteroatom group-containing radicals is substituted (for example, hydroxyl groups) is expressly noted.

The radicals R ¹ Preferably, the monovalent organic radical R ¹ , which is free of carboxy, hydroxy, thiol, imino and primary and secondary amino groups, for an aliphatic radical having 1 to 100, particularly preferably 1 to 50 and all more preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, an aromatic radical of 6 to 20, more preferably 1 to 16 and most preferably 1 to 12 carbon atoms, or an aliphatic radical of 7 to 30, more preferably 7 to 20 and especially preferred zugt 7 to 12 carbon atoms. Insofar as the radicals mentioned satisfy the above conditions, they may by definition also contain heteroatoms such as, for example, polyoxazoline radicals. If the monohydric organic radical R ¹ is an aliphatic radical, this is preferably a branched or unbranched, saturated hydrocarbon radical having 1 to 40, more preferably 1 to 20 and most preferably 1 to 10 carbon atoms, or it is a branched or unbranched, unsaturated hydrocarbon radical having 2 to 40, more preferably 2 to 20 and most preferably 2 to 10 carbon atoms.

Aliphatic or vinyl-containing radicals can also be used as the aliphatic ethylenically unsaturated radicals R ¹ . A subgroup of the last-mentioned radicals are, for example, radicals R ¹ which contain acrylic or methacrylic radicals, for example the radicals H 2 C =CH- (CO) -O-CH 2 CH 2 or

H ₂ C = C (CH 3) - (CO) -O-CH ₂ CH ₂ . The incorporation of such radicals allows, for example, the solid incorporation of the polyethers of the formula (I) in radiation-curing compositions, in particular radiation-curable coating compositions.

If the monovalent organic radical R ¹ is an aromatic radical, this is preferably a hydrocarbon radical having 6 to 20, particularly preferably 6 to 16 and very particularly preferably 6 to 10 carbon atoms. The aromatic radical may hereby carry as substituents aliphatic hydrocarbon radicals, the carbon number of which is contained in the abovementioned number of carbon atoms of the aromatic radical. For example, a methylphenyl radical is an aromatic radical of 7 carbon atoms. If the monovalent organic radical R ¹ is an araliphatic radical, it is preferably a hydrocarbon radical having 7 to 30, particularly preferably 7 to 20 and very particularly preferably 7 to 12 carbon atoms. A phenylmethyl radical, also called benzyl radical, is for example a Araliphatic residue with 7 carbon atoms. In this case, the radical may carry as substituents further aliphatic hydrocarbon radicals, for example, on the aromatic ring, the carbon number of which is contained in the abovementioned number of carbon atoms of the araliphatic radical. For example, a p-methylbenzyl radical is an araliphatic radical of 8 carbon atoms.

In the context of the present invention, as radicals R ^{1 it is} preferred to realize the abovementioned aliphatic radicals, in particular the abovementioned saturated aliphatic radicals and very particularly the abovementioned preferred, particularly preferred and very particularly preferred aliphatic hydrocarbon radicals in the general structure of the formula (I). These are particularly preferably heteroatom-free.

The radicals R ² (for u = 0)

When u = 0, R ^{2 is} a bivalent organic radical of the formula CHR ^2a CHR ^2b . Preferably herein at least one of R ^2a and R ^{2b is}

Hydrogen.

If u = 0, both radicals R ^2a and R ^{2b are} hydrogen, the radical CHR ^2a CHR ^2b is an ethylene radical CH ₂ CH ₂ . If u = 0, but only one of R ^2a and R ^{2b is} hydrogen, then the second, non-hydrogen radical is preferably a branched or unbranched, saturated or unsaturated, preferably saturated, aliphatic radical having 1 to 20, preferably 1 to 16, more preferably 1 to 10 or 1 to 9 carbon atoms, an aromatic radical having 6 to 16, more preferably 6 to 12 and most preferably 6 to 10 carbon atoms, or an araliphatic radical having 7 to 18, preferably 7 to 14 and more preferably 7 to 12 carbon atoms. When u = 0, and exactly one of R ^2a and R ^{2b is} hydrogen, among the aforementioned aliphatic groups, those which are preferably saturated hydrocarbon groups of 1 to 20, preferably 1 to 16 are particularly preferable 1 to 10 or 1 to 9 carbon atoms. If exactly one of the radicals R ^2a or R ^{2b is} hydrogen and the other is a methyl group, then the radical CHR ^2a CHR ^2b is an i-propylene radical.

The aliphatic, preferably saturated, hydrocarbon radicals may also contain one or more ether oxygen atoms -O- and / or one or more carboxylic acid ester groups -O-C (= O) -. Other heteroatoms, in particular nitrogen atoms, are preferably not contained in these radicals. are

Contain ether oxygen atoms or carboxylic acid ester groups, so in the corresponding radical preferably contains exactly one ether oxygen atom or exactly one carboxylic acid ester group. In the case of a carboxylic acid ester group, their carbon atom counts to the total number of carbon atoms of the residue. The aforementioned preferred aliphatic radicals R ^2a or R ^2b are particularly preferably hydrocarbon radicals which contain no ether oxygen atom and no carboxylic acid ester group, or which contain exactly one ether oxygen atom or one carboxylic acid ester group.

If the aliphatic, aromatic or araliphatic radicals R ^2a or R ^2b are those having exactly one ether oxygen atom or exactly one carboxylic acid ester group, these radicals particularly preferably have the following formula: CH 2 -O [CO] iR ^2c , where i is 0 or 1 R ^{2c is} a hydrocarbon radical having 1 to 18, preferably 1 to 14 and particularly preferably 1 to 10 carbon atoms. If i = 0, the radical R ^{2c contains} exactly one ether oxygen atom; if i = 1, the radical R ^{2c contains} exactly one carboxylic acid ester group. Most preferably, i = 0 in these groups.

When the hydrocarbon radical R ^{2c is} an aliphatic radical, this is unbranched or branched. If the hydrocarbon radical R ^{2c is} aliphatically unbranched, it preferably contains 1 to 19, particularly preferably 1 to 15 or very particularly preferably 1 to 9 or 1 to 8 carbon atoms. If the radical R ^{2c is} branched aliphatically, it preferably contains 3 to 19, particularly preferably 3 to 15 or very particularly preferably 3 to 9 or 4 to 8 carbon atoms.

When the hydrocarbon radical R ^{2c is} an aromatic radical, it preferably contains 6 to 14, particularly preferably 6 to 12 or very particularly preferably

6 to 10 carbon atoms. When the hydrocarbon radical R ^{2c is} an araliphatic radical, it preferably contains 7 to 16, particularly preferably 7 to 12 or very particularly preferably

7 to 10 carbon atoms.

In the polyethers of the formula (I), at least one of the radicals R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 is} an aromatic or araliphatic radical. Therefore, if none of the radicals R ³ , R ³ ⁴ , R ⁵ , R ⁶ , R ⁷ or R ^{8 is} an aromatic or

Araliphatic radical is or contains such, the radical R ² must contain an aromatic or araliphatic radical in such a case. In such a case it is preferred that for at least one radical [OR ² ], the radical R ^{2 is} a radical CHR ^2a CHR ^2b in which R ^2a or R ^{2b is} hydrogen and the other of the two radicals is CH 2 -O [CO] iR ^2c , wherein R ^{2c is} an aromatic radical having 6 to 14 carbon atoms, preferably 6 to 10 or 6 to 8 carbon atoms, and particularly preferably represents a phenyl radical.

If, in formula (I), different types of CHR ^2a CHR ^2b are present for u = 0, these may be arranged in blocks, randomly or gradient-like. If, for example, v = 20, then for 10 of the 20 radicals CHR ^2a CHR ^2b , it holds that R ^2a = R ^2b = H and for the remaining 10 of the 20 radicals CHR ^2a CHR ^2b that R ^2a = H and R ^2b = CH3 , then the radical (OR ² ) 2o is an ethylene oxide / propylene oxide radical having 10 ethylene oxide and 10 propylene oxide units each, these 20 units may be arranged in two or more blocks, random or gradient. The radicals R ² (for u = 1) When u = 1, R ^{2 is} preferably a branched or unbranched, saturated or unsaturated, preferably saturated, aliphatic hydrocarbon radical having 2 to 24, more preferably 2 to 16, more preferably 2 to 8 and most preferably 4 or 5 carbon atoms. If different types of radicals R ² are represented in formula (I) for u = 1, these may be arranged in blocks, statistically or in a gradient-like manner.

The radicals R ² , when u = 0 and u = 1 are realized simultaneously in formula (!) Holds simultaneously for a part of the v radicals [O- (C = O) _u -R ² ] that u = 0 and for the others of the v radicals [O- (C = O) _u -R ² ], that u = 1, the above statements apply equally. In addition, the [OR ² ] and [O- (C = O) -R ² ] residues are also arranged in blocks, randomly or gradient-like. However, it is preferred that the [OR ² ] radicals and [O- (C = O) -R ² ] radicals are present in separate blocks. Within this preferred arrangement, the [OR ² ] residues in their block or blocks are also blocky or random, and the [O- (C = O) -R ² ] residues are preferably block-like or random within their block or blocks in front. Preferably, at least one of the blocks for the u = 1 is bound to the radical R ¹ .

In general, for the radicals [O- (C =O) _u -R ² ], it is preferred that when u = 0.

The radicals R ³ , R ⁴ , R ⁷ and R ⁸ The radicals R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen or monovalent organic radicals, the latter being selected from the group consisting of aliphatic radicals with 1 to 8 carbon atoms, aromatic Radicals having 6 to 8 carbon atoms, or araliphatic radicals having 7 to 10 carbon atoms.

The radicals R ³ , R ⁴ , R ⁷ and R ⁸ are particularly preferably hydrogen or an unbranched alkyl radical having 1 to 8 carbon atoms or a branched alkyl radical having 3 to 8 carbon atoms. Most preferably, the radicals R ³ , R ⁴ , R ⁷ and R ^{8 are} hydrogen and / or methyl, most preferably hydrogen. The rest R ⁵

The radical R ⁵ is a radical R ^5a or R ^5b .

Here R ^{5a is} a monovalent organic radical which is free of carboxy, hydroxy, thiol, imino and primary and secondary amino groups and which is preferably selected from the group consisting of aliphatic hydrocarbon radicals having 1 to 20 carbon atoms, aromatic hydrocarbon radicals 6 to 12 carbon atoms and araliphatic hydrocarbon radicals having 7 to 24 carbon atoms, wherein all of the abovementioned hydrocarbon radicals may contain one ether oxygen atom. Hydrogen atoms in the radicals may be substituted by halogen atoms, preferably chlorine atoms, where, if a corresponding substitution is present, monochloro-substituted radicals are preferred. Particularly preferred R ^{5a is} a branched or unbranched radical CH ₂ -O- (Ci-io-alkyl) or a radical CH ₂ -O-phenyl.

Contains the radical R ^5a an ether oxygen atom, this is preferably a radical -CH 2 OR ^5d, ^5d wherein R is a monovalent organic radical which is free of ether oxygen atoms and carboxyl, hydroxyl, thiol, imino and primary and secondary amino groups and which is preferably selected from the group consisting of aliphatic hydrocarbon radicals having 1 to 8 carbon atoms. atoms, aromatic hydrocarbon radicals having 6 to 8 carbon atoms, araliphatic hydrocarbon radicals having 7 to 20 carbon atoms. However, the radical R ^5d may for example be attached to the oxygen atom in the radical -CH 2 OR ^5d C = O a radical R ^5d this attributable group. The radical R ^{5d may,} for example, also be a radical -S (= O) 2-phenyl.

If none of the radicals R ² , R ³ , R ⁴ , R ^5b , R ⁶ , R ⁷ or R ⁸ is or contains an aromatic or araliphatic radical, in such a case the radical R ^{5a must be} an aromatic or araliphatic radical or contain such. In such a case, it is preferred if the residue R ^5a represents a radical CH2-OR ^5d, wherein R ^5d represents an aromatic radical having 6 to 14

Carbon atoms, preferably 6 to 10 or 6 to 8 carbon atoms, and particularly preferably represents a phenyl radical.

The radical R ^5b is a radical CH 2 -OR ^5c in which R ^{5c is} hydrogen or a monovalent one or more hydroxyl-containing organic radical which preferably contains one or more ether oxygen atoms and is selected from the group consisting of aliphatic radicals with 1 to 24 carbon atoms, aromatic radicals having 6 to 14 carbon atoms, and araliphatic radicals having 7 to 18 carbon atoms.

If the radical R ^5b is a monovalent, one or more hydroxyl groups and one or more ethers containing oxygen, this radical can be prepared starting from a radical R ^5b = CH 2 -OR ^5c with R ^5c = H, ie a radical CH 2 OH, for example, by ring-opening polymerization of oxiranes, lactones, lactides or oxetanes, in particular also hydroxyoxetanes or by condensation of hydroxycarboxylic acids build. Species suitable for this purpose are listed below under the general formulas (IV), (V), (Va), (Vb) and (VII).

If R ^{5c is} hydrogen, it is preferred for at most 50% of the v + w units, particularly preferably 1 to 30% and very particularly preferably 1 to 20% of the units v + w applies. In other words, if, for example, v + w = 4 + 12 = 16, then preferably not more than 8 units of the 12 "w units" R ^{5c should be} hydrogen, of which preferred R ^5b are those which Among these, in turn, preference is given to those whose ether oxygen atom (s) are linked by 2 or 3 carbon atoms in the shortest chain to another ether oxygen atom or an OH group, that is, independently of possible substituents or hydrogen atoms on the carbon atoms have the following motifs: -O ^* -CCO ^** - or -O ^* -CCCO ^** - Here is the oxygen atom marked with a ^* for the at least one ether oxygen atom and the If the OH groups are partially or completely OT., the oxygen atom in an OH group is denoted by ^** for another ether oxygen atom or the oxygen atom transferred, the above statement for OH groups also applies to radicals OT.

Most preferably, the one or more ether oxygen atoms u and one or more hydroxyl-containing organic radical R ^{5c is} a radical of the general formula (II):

(II) wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} independently defined as above or below, and p is 1 to 10, preferably 1 to 6 and particularly preferably 1 to 3 stands. Preferably, w + p stands for a value of <30, more preferably for a value of 1 to 20, very particularly preferably for a value of 1 to 10 and even better for a value of 1 to 8, 1 to 6 or 1 to 5 , Such radicals can be introduced by addition of oxiranes of the general formula (VII) given below to a hydroxyl radical, in particular the hydroxyl radical in the formula CH ₂ -OR ^5c with R ^5c = H, ie CH ₂ -OH. The rest R ⁶

When R ^{5 is} R ^5b , R ^{6 is} preferably defined as R ^5a or it is hydrogen. Particularly preferably, the radical R ^{6 is} an alkyl radical having 1 to 10, very particularly preferably 2 to 6 and more preferably 2 to 4, in particular 2 carbon atoms.

Connected radicals R ⁵ and R ⁶

It is also possible that the radicals R ⁵ and R ^{6 are joined} together by ring closure. Such rings preferably contain 4 or 5 carbon atoms and optionally an N-alkylated nitrogen atom.

The radicals R ⁹ in the general formulas (I) and (II) The radical R ⁹ is hydrogen or a monovalent organic radical selected from the group consisting of aliphatic radicals having 1 to 24 carbon atoms, aromatic radicals having 6 to 14 carbon atoms, araliphatic radicals having 7 to 18 carbon atoms, or a radical T selected from the group consisting of P (O) (OH) _2- x (O © Z ©) _x , S (O ₂ ) (OH) i _-y (O © Z ©) _y, wherein x is 0, 1 or 2 and y is 0 or 1, and (C = O) _s - (NH) _t -T ^a wherein s is 0 or 1 and t is 0 or 1 and in the case that s = 0 also applies t = 0, and in which T ^{a is} a monovalent organic radical having 1 to 100 carbon atoms, which may optionally have one or more of the following radicals COO © Z ®, -OP (O) (OH) _2- x (O © Z ©) _x and

-OS (O ₂₎ contains (OH) i _-y (O ^Θ Z ©) _y, with the above definitions, and the radicals Z © independently of one another represent an alkali metal cation, preferably Li ^+, Na ⁺ or K ^+, a cation of the formula ⁺ N (R ^9a ) ₄ in which the radicals R ^9a independently of one another represent hydrogen or an organic radical. Are all four radicals R ^9a for Hydrogen, it is an ammonium ion. If all radicals R ^{9a are} hydrocarbon radicals, preferably hydrocarbon radicals having 1 to 10 carbon atoms, this is referred to as a particular embodiment of a quaternary ammonium radical.

If the radical R ^{9 is} an aliphatic radical having 1 to 24 carbon atoms, it is particularly preferably a radical of the formula: [R ^9b (CO) _m O] _n R ^9c , where R ^9b is defined as R ² , R ^9c is hydrogen or as T is defined, m is defined as u and n is defined as v, wherein R ^{9b is} independently selected from R ² , R ^{9c is} independently selected from T, m is independently selected, and n is independently of v is selected.

Substitution of hydroxyl groups by groups OT As defined above, up to 100 mol%, if present preferably 10% to 100 mol%, particularly preferably 20 or 30% to 100 mol% of the above R ^5b and R ⁹ or by elimination of hydrolytically cleavable radicals resulting hydroxyl groups by (i) radicals -Ο-Ρ (Ο) (ΟΗ) ₂ -χ (Ο ® Ζ ©) _χ , (ii) radicals -OS (O ₂ ) (OH) i _-y (OOZ ©) y and / or (iii) -O- (C = O) _s - (NH) _t -T ^a substituted (defini- tions of the radicals as above) to be. Although various radicals (i), (ii) and (iii) can be realized in a species of formula (I), it is usually preferred that only one or two types of radicals (i), (ii) or (iii ) are present in a polyether of formula (I). All percentages also represent limits for (i), (ii) and (iii), alone. In other words, this means that if the hydroxyl radicals are completely or partially replaced by radicals (i) -O-

P (O) (OH) ₂ -x (O © Z ©) x is replaced by the limits "10 to 100 mol%", "20% to 100 mol%", and "30% to 100 mol%" However, it is also conceivable that, for example, in each case 5 mol% of the hydroxyl groups are replaced by species (i) and (ii), which in total also realizes the lower limit of 10 mol%.

The values for v, w and p In each individual species of the general formula (I), integer values for v, w and p are realized. Especially at low values of v, w and p, the polyether of the general formula (I) can be a molecularly uniform product in which the number-average and the weight-average molecular weights are identical. At higher values of v, w and p, it may be possible to specify only a mean value for v, w and p, which corresponds to the number average of the individual species. If there are number-average values for v, w and p, they must be in the limits specified for the values v, w and p. Preferably, the value of v = 1 to 50, more preferably v is a value of 2 to 45, most preferably from 6 to 40.

The value for w is preferably from 1 to 15, more preferably v is from 1 to 10, very particularly preferably from 1 to 6.

molecular weights

The polyethers of the general formula (I) preferably have a weight-average molecular weight M _w (determined by GPC as indicated in the experimental part) of from 400 to 5000 g / mol, particularly preferably from 600 to 4000 g / mol, very particularly preferably from 800 to 3000 g / mol. The polydispersity PD, which can likewise be determined by means of GPC, is preferably from 1:05 to 2.0, particularly preferably from 1:05 to 1, 6 and very particularly preferably from 1 to 1 to 4. Particularly preferred polyethers of the formula (I)

Although the abovementioned radicals and values of the indices can in principle be freely combined in the abovementioned ranges, in particular in order to be able to adapt hydrophilic and hydrophobic regions well to the particular application profile of the polyethers of the formula (I) or the wetting and dispersing agents according to the invention, the range of pigmented compositions, in particular pigmented coating compositions, the combinations listed below are found to be particularly advantageous. Particular preference is given in the polyethers of the formula (I):

R ^{1 is} a branched or unbranched alkyl radical having 1 to 20, more preferably 1 to 16 or 1 to 12 carbon atoms,

u preferably 0,

R ² preferably represents ethylene radicals, propylene radicals and / or Ch Ch Ch -O-phenyl) radicals,

v is preferably from 4 to 50, more preferably from 6 to 40,

R ³ , R ⁴ , R ⁷ and R ^{8 are} preferably hydrogen,

R ⁵ preferably represents a radical R ^5b , that is to say a radical CH 2 -OR ^5c in which R ^{5c is} preferably hydrogen, a monovalent aliphatic hydrocarbon radical which preferably contains 2 to 24 carbon atoms and which optionally contains one or more hydroxyl groups and one or more contains several oxygen atoms, or an aromatic radical having 6 to 8 carbon atoms, is,

R ^{6 is} preferably an alkyl radical having 1 to 6, more preferably 2 to 5 and most preferably having 2, 3 or 4 carbon atoms, and

R ^{9 is} preferably H, where preferably 0 to 100 mol% of the hydroxyl groups formed via the above R ^5b and R ⁹ radicals or by cleavage of hydrolytically cleavable radicals can only be replaced by groups Ρ (Ο) (ΟΗ) 2 (Ο ^Θ Ζ ©) _{χ are} replaced, and wherein x and Z ^{+ are} as defined above.

Particularly preferably, all of the hydroxyl groups formed via the above R ^5b and R ⁹ radicals or by elimination of hydrolytically removable radicals are present as hydroxyl groups. This applies in particular if the polyethers of the formula (I) according to the invention or the wetting agents and dispersants according to the invention are to be used for the preparation of pigmented compositions, for example pigmented millbases or pigment pastes. Such millbases and pigment pastes can usually be prepared without additional binders, which makes them particularly universally applicable, especially in the production of pigmented coating compositions. Wetting and / or dispersing agent containing or consisting of the polyethers according to the invention

The present invention also relates to wetting and / or dispersing agents, containing or consisting of one or more polyethers of the general formula (I). These are also referred to as wetting and / or dispersing agents according to the invention.

The wetting and / or dispersing agents are prepared as set out in the following section. Preferably, these wetting and dispersing agents consist of

Polyethers of the general formula (I). However, the wetting and / or dispersing agents may also be present in dissolved form. If storage stability is required, solvents which are inert to the dissolved solids are used to prepare such solutions. Suitable organic solvents are, for example, ethers, esters, aromatic and aliphatic hydrocarbons, but it is also possible to use water. Also possible is a solution of the wetting and / or dispersing agents according to the invention in ethylenically unsaturated monomeric compounds (so-called reactive diluents). It is also possible to use the solvents mentioned in the context of the synthesis of the polyethers of the formula (I) or mixtures thereof.

The wetting and / or dispersing agent prepared according to the synthesis shown below may contain by-products, so that the reaction product may not be up to 100 wt .-% of species of the general formula (I). Preferably, the species of the general formula (I) is the main constituent of the reaction product, that is, by the synthesis described below, reaction products preferably containing more than 50% by weight, more preferably at least 60 or at least 65% by weight .-%, and most preferably at least 70 wt .-%, based on the weight of the reaction product of species which fall under the formula (I). Since the reference point is the weight of the reaction product, this does not include the initial weight of solvents and possibly set, not chemically bound in the reaction product excipients such as catalysts. The percentages by weight are thus based on the sum of the weighings of the reactants, less any resulting elimination products such as water of reaction or alcohols. In the optimal case, the reaction products consist of species of the general formula (I). If by-products are included, they usually need not be separated. In such cases, the reaction product, including any by-products, is used as wetting and / or dispersing agent.

Process for the preparation of the wetting and dispersing agents according to the invention or the polyethers of the general formula (I)

The polyethers of the formula (I) used according to the invention or the wetting agents and dispersants containing them or consisting thereof are preferably obtained by polymerization with ring opening, very particularly preferably by cationic polymerization with ring opening. The cationic polymerization is carried out by customary methods known to the person skilled in the art. Suitable process parameters, catalysts and reaction media can be found inter alia in WO 2002/040572 A1 and the citations listed there.

In the following examples, the preparation of the polyethers of the formula (I) used in accordance with the invention or the wetting and dispersing agents according to the invention containing them and illustrated by corresponding process schemes are described in general form.

The terms used below and the use of the indices correspond to all the above definitions of the radicals with respect to

Polyether of the formula (I). Thus, for example, the radical R ¹ in the formula (I) corresponds to the radical R ¹ in the formula R ¹ OH. Thus, all the following terms are identical to the terms of formula (I). In that regard, specified for the manufacturing process particular embodiments of the radicals and indices defined in formula (I) These are also considered to be particular embodiments of the formula (I). This applies equally to the radicals directly derivable from the specific compounds. The preparation of the polyethers of the formula (I) according to the invention or of the wetting and dispersing agents according to the invention which comprise them or of these according to the invention is typically based on monoalcohols of the formula (III): R ¹ -OH (III)

The radical R ¹ is a monovalent organic radical having 1 to 100 carbon atoms. Preferred embodiments of this residue "The radicals R ^1" are listed in the above heading. This residue may for example also of the groups (OR ²⁾ contain different polyether or Polyoxazolingrup- pen, but is preferably free of heteroatoms.

The structure of the structural units [O- (C = O) _u -R ² ] v is preferably carried out by ring-opening reactions of oxiranes of the formula (IV) for u = 0:

wherein R ^2a and R ^{2b are} independently hydrogen, an aliphatic radical having 1 to 20 carbon atoms, an aromatic radical having 6 to 10 carbon atoms, or an araliphatic radical having 7 to 10 carbon atoms. Preferred embodiments of the radicals R ^2a and R ^2b are listed under the above heading "The radicals R ² ".

The adducts obtained by adding species of general formula (IV) to the species of general formula (III) can be prepared using a Zigen species of formula (IV) or different species of formula (IV) can be obtained. In the latter case, the different species can be used simultaneously, which usually leads to a statistical distribution, or sequentially, which usually leads to a block-like structure, or in a dosage in which a species of formula (IV) initially in excess is used against a plurality of other species of the formula (IV) and is present later in deficit, which usually leads to a gradient-like structure. When R ^2a and R ^{2b are} each hydrogen, the units [OR ² ] are ethylene oxide units. When R ^2a is hydrogen and R ^2b is a methyl group, the units [OR ² ] are propylene oxide units. The particularly preferred products obtained therefrom are accordingly R ¹ -capped polyethylene oxides, R ¹ -capped polypropylene oxides or R ¹ -capped random, block-like or gradient-like

Poly (ethylene oxide / propylene oxide) adducts.

The adducts of (III) and (IV) used as starting units for the Oxetanpolymerisation can also be selected from alkoxylated alcohols. Such alkoxy-Herten monoalcohols (for example, available under the trade name Luten sol® from BASF SE, Ludwigshafen) are prepared by basic-catalyzed ring opening of ethylene oxide or propylene oxide or both of alcohols, such as methanol, butanol, n-decanol, iso-decanol , Oleyl alcohol, behenyl alcohol or Guerbet alcohols. Basic alkoxylation catalysts used are generally KOH, NaOH, CsOH or KOtBu and NaOCH ₃ . It is usually carried out at temperatures between 80 and 140 ° C and at pressures between 2 and 10 bar.

The construction of the structural units [O- (C = O) _u -R ² ] v can also be achieved by

Ring-opening polymerization of lactones of formula (V) for u = 1:

wherein R ^{2 is} as defined above, and particularly preferably represents an aliphatic hydrocarbon radical having 4 to 6 carbon atoms.

Also usable, but less preferred because of the liberated water of reaction, are the hydroxycarboxylic acids (Va), which can be bound by condensation reaction to terminal hydroxyl groups, for example of the formula (III)

The hydroxyl group bonded in the general formula (Va) to the self-hydroxyl group-free radical R ² may be bonded at any position in the radical R ² . In question are, for example, the unsaturated hydroxycarboxylic acids which are present in castor oil or their hydrogenated analogs such as 12-hydroxystearic acid.

Also usable are the cyclic diesters of alpha-hydroxycarboxylic acids (also referred to as lactides) as shown in formula (Vb).

An example of this is the diester of lactic acid, where R ^{2 is} CH-CH 3. R ² preferred embodiments of the radicals under the above heading "The residues R2" section. The by single or multiple addition of species of the general formula (V) and (Vb), or single or multiple condensation of the species of formula (Va) obtained on the compounds of general formula (III)

Adducts can be obtained using one or more species of formula (V), (Va) and (Vb). If several different species are used at the same time, this usually leads to a statistical distribution of the residues within the forming chain; if they are used successively, this generally leads to a block-like structure. If they are metered in such a way that one species of the formula (V), (Va) or (Vb) is initially used in excess over a plurality of other species and this is later deficient, this usually leads to a gradient-like structure.

If R ² is a radical (Ch K then the species of general formula (V) is epsilon-caprolactone and formula (Va) is 6-hydroxyhexanoic acid.) R ² is a radical (CH2) 4, the species of the general formula (V) is delta-valerolactone or, in the case of the formula (Va), 5-hydroxyvaleric acid, the preferred products obtained therefrom being correspondingly R ¹ -capped polycaprolactones, R ¹ - capped polyvalerolactones or R ¹ -coded random, blocky or gradient poly (caprolactone / valerolactone) adducts.

It is also possible first to react one or more compounds of the general formula (III) with one or more species of the formula (IV) and then to react the resulting adduct with one or more species of the formula (V), (Va) and / or (Vb ).

It is likewise possible that initially one or more compounds of the general formula (III) having one or more species of the formula (V), (Va) and / or (Vb) are reacted and then the resulting adduct with one or more species of the formula (IV).

In the aforementioned manner, for example, block-structured structures of polyether blocks (u = 0) and polyester blocks (u = 1) can be constructed, which in turn can be constructed statistically, block-like or gradient-like within the blocks, as shown above. It may also be several polyether and / or polyester blocks alternate. By the choice of the compound of formula (III) and of the oxirane of formula (IV) or the species of formula (V), (Va) and / or (Vb) hydrophilic and hydrophobic structures can also be within the species of the following formula ( VI) combine. The products obtained preferably have the following structure of the formula (VI):

In turn, one or more oxetanes of the formula (VII) can be added to the species of the formula (VI):

The radicals R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined under formula (I). Preferred embodiments of the radicals R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are described under the above headings "The radicals R ³ , R ⁴ , R ⁷ and R ⁸ ", "The radical R ⁵ " and The radical / ^ "or" Connected radicals R ⁵ and R ⁶ "are listed.

Most preferably, the radicals R ³ , R ⁴ , R ⁷ and R ^{8 are} methyl or hydrogen, most preferably hydrogen.

Preferred examples of radicals R ^5a are linear alkyl radicals having 1 to 20, preferably 2 to 10 or 2 to 8 carbon atoms, branched or cyclic alkyl radicals having 3 to 20, preferably 4 to 10 carbon atoms, aryl radicals having 6 to 10 carbon atoms, arylalkyl radicals with 7 to 14 carbon atoms, alkylaryl radicals having 7 to 14 carbon atoms. Hydrogen atoms in these radicals may be replaced by halogen atoms. If so, the halogen is preferably chlorine. Preferably, only one hydrogen atom is replaced by a halogen atom. However, R ^5a preferably does not contain any halogen atoms.

Likewise preferred radicals R ^5a are radicals CH 2 -OR ^5d , in which R ^{5d is} a radical R ^5a , in particular one of the radicals R ^5a mentioned as preferred in the preceding paragraph. If the group R ^5d is an alkyl group which can easily be split off under hydrolysis conditions, for example a tert-butyl group, this can also be split off after the addition reaction, a group R ^{5b of} the formula CH 2 -OH being formed. The person skilled in the art knows further easily removable groups, which are also referred to as protective groups. The hydroxyl groups thus obtained are also among the hydroxyl groups to be replaced by radicals OT of 10 to 100 mol%.

Commercially available compounds of this type are, for example, 3-ethyl-3- ((phenoxy) methyl) oxetanes (OXT-21 1, available from Toagosei Co., Ltd., Japan) and 3-ethyl-3 - ((2-ethylhexyloxy ) methyl) oxetanes (OXT-212, available from

Toagosei Co., Ltd., Japan). Most preferably, R ^{5 is} a radical R ^5b and R ^{6 is} R ^5a .

Usually, the cationic polymerization of oxetanes of the formula (VII) is carried out on species of the formula (VI) or preferably in-situ formed hydroxyl groups in species of the formula (I) with ring opening in the presence of a catalyst without addition of a solvent. However, the polymerization can also be carried out with the concomitant use of a solvent which is inert under the polymerization conditions, as described in detail below. Depending on the order of addition of the ring-opening cationically polymerizable species of the formula (VII), a random, blocky or gradient-like structure can be used within the remainder

[C (R ³⁾ (R ⁴⁾ -C (R ⁵⁾ (R ⁶⁾ -C (R ⁷⁾ (R ⁸⁾ -O] _w can be obtained. Index w is as defined in formula (I).

Reaction of the species of the formula (VI) with species of the formula (VII) results in species of the formula (I) where R ⁹ = H, ie a terminal hydroxyl group.

If, in addition, species of the general formula (I) with R ⁵ = R ^5b are used, then species result which contain further hydroxyl groups introduced via the radical R ^5b . These hydroxyl groups are not terminal in the polyethers of the formula (I) but are present as hydroxy-functional side groups on the polyether backbone of the polyether (I).

Oxiranes of the formula (IV), lactones of the formula (V) or oxetanes of the formula (VI) can in turn be added to these lateral hydroxyl groups in the radicals R ^5b but also to the terminal hydroxyl group OR ⁹ where R ⁹ = H so that from the hydroxyl groups containing side groups on the polyether finally hydroxyl groups and ether oxygen atoms containing side chains can be generated or the terminal hydroxyl group OR ^{9 is} modified with R ⁹ = H to form at least one further hydroxyl group.

If the oxiranes of the formula (IV) thus added to a pendant or terminal hydroxyl group, species of the formulas (V), (Va) and (Vb) or oxetanes of the formula (VI) themselves contain no hydroxyl groups, then the side chains remain monohydroxy-functional or the main chain is extended.

However, if the oxtetanes of the formula (VI) added to a pendant or terminal hydroxyl group themselves contain hydroxyl groups (these oxetanes are also called hydroxyoxetanes in the following), the addition of such a hydroxyoxetane will not only result in the already existing hydroxyl group being replaced by ring opening, but instead also the introduction of the hydroxyl group or hydroxyl groups already present on the hydroxyoxetane. Further oxiranes of the formula (IV), species of the formulas (V), (Va) and / or (Vb) or oxtetanes of the formula (VI), in particular, may be added both to the hydroxyl groups already present on the hydroxyoxetane and those already present on the hydroxyoxetane Oxetanes of the formula (VI), which are themselves hydroxy-functional, preferably monohydroxy-functional added. In this case, branched, preferably hyperbranched, or quasi-dendritic hydroxyoxetane-based structures can be synthesized on the polyether of the formula (I), pendant or terminal. Whether only a single or a few lateral or terminal hydroxyl groups are to be formed by addition of a hydroxyoxetane or branched or highly branched structures are to be generated can be controlled by the amount of hydroxyoxetanes used. It may also be advantageous for a hydroxyoxetane-based block to be initiated by a hydrophobic oxetane containing hydroxyl groups.

The polyethers of the formula (I) thus obtained are monohydric-functional or polyhydroxy-functional as a function of the use or "non-use" of hydroxy-functional oxetanes, it also being possible for the hydroxyl groups to be completely or partially replaced by groups OT as described below. In general, it can be stated that in the event that strictly linear polyethers of the formula (I) are to be obtained, no hydroxyoxetanes are used, ie no oxetanes of the formula (VII) with the radical R ^5b are used. Such species have more hydrophobic properties in the polyoxetane section (s). In order to nevertheless produce an amphiphilic species of formula (I), in such a case preferably R ^2a and R ^{2b will be} hydrogen. That is, the polyoxetane portion (s) are introduced through hydrophilic polyethylene oxide portions.

The polyethers of the formula (I) in which the hydroxyl group or the hydroxyl groups are not replaced by radicals OT are already suitable as wetting and dispersing agents. They can be used particularly advantageously in coating compositions, in particular pigmented coating compositions. However, they also serve as intermediates in the preparation of polyethers of the formula (I) in which existing hydroxyl groups are completely or partially replaced by groups OT. Such radicals OT-containing polyethers of the formula (I) can also be used in coating compositions, but in particular also in high-solids or solvent-free systems, and particularly preferably in SMC and BMC.

According to the definition of the polyethers of the formula (I), 0 to 100 mol% of the hydroxyl groups in the radicals R ^5b and R ^{9 may be} replaced by a radical OT selected from the group consisting of

(i) radicals -OP (O) (OH) _2-x (O © Z ©) _x , where x is 0, 1 or 2,

(ii) residues -OS (O ₂₎ (OH) i _-y (O ^Θ © Z) _y wherein y is 0 or 1, and

(iii) residues -O- (C = O) _s - (NH) _t -T ^a wherein s is 0 or 1 and t is 0 or 1, and in the case that s = 0 and t = 0, and wherein T ^{a is} a monovalent organic radical having 1 to 100, preferably 1 to 50, more preferably 1 to 30 or 1 to 20 and most preferably 1 to 10

Carbon atoms which optionally contains one or more of the following radicals COO® Z®, COOH and -S (O ₂ ) (OH) i _-y (O ^QZ ©) y, and wherein the above Z.sup.d, independently of one another, are alkali metal cations, an ammonium ion or protonated or quaternized amines.

The mentioned under (i) residues -Ο-Ρ (Ο) (ΟΗ) 2 ^(Ο Θ Ζ ©) _χ can be introduced for example by a total or partial phosphorylation of the hydroxyl groups with polyphosphoric acid, polyphosphoric acids or phosphoric acid chlorides.

To introduce the mentioned under (ii) residues -OS (O2) (OH) i _-y (O ⁰ © Z) _y, the hydroxyl groups with the aid of concentrated sulfuric acid, oleum,

Sulfur trioxide or chlorosulfonic acid are reacted.

Other methods for introducing sulfonic acid groups (ii) and phosphoric acid groups (i) are described, for example, in the Journal of Polymer Science: Part A: Polymer Chemistry 2001, 39, 955-963.

The introduction of the radicals (iii) -O- (C = O) _s - (NH) ^a tT can also be done in several ways. In the case where s = t = 1, the hydroxyl groups can be reacted with an isocyanate of the formula T ^a -N = C = O. By modifying with longer-chain alkyl isocyanates, such as stearyl isocyanate, the polarity of the polymer can be changed in the direction of hydrophobicity, whereby, for example, a use of the polymers in non-polar thermoplastics is facilitated. In contrast, one achieves an increase in the hydrophilicity and optionally improved water solubility in that free hydroxyl groups of the polyether of the formula (I) are completely or partially reacted with hydrophilic compounds, for example with tolylene diisocyanate monoadducts. Suitable examples are monoadducts obtained from the reaction of toluene diisocyanate (TDI) with methanol-started polyethylene glycol. By means of appropriate mixtures of hydrophilic and hydrophobic modifications, it is also possible to prepare amphiphilic polyethers of the formula (I).

The introduction of the radicals (iii) -O- (C = O) _s - (NH) t T ^a with s = 1 and t = 0, for example, by reacting free hydroxyl groups on polyethers of the formula (I) with mono- or polycarboxylic acids, or their anhydrides, halides, in particular chlorides or esters possible.

For example, free hydroxyl groups can be completely or partially esterified with acetic acid, in which case T ^{a is} a methyl group.

By using polycarboxylic acids, their anhydrides, halides, in particular chlorides or esters instead of the abovementioned monocarboxylic acids, their anhydrides, halides, in particular chlorides or esters, radicals T ^{a can be} introduced which contain a COO ^{Θ Z®} radical. Particularly suitable polycarboxylic acids or their anhydrides are cyclic carboxylic acid anhydrides, such as maleic anhydride, succinic anhydride and trimellitic anhydride.

The polyethers of the formula (I) used according to the invention preferably have no ester groups, with the exception of the abovementioned succinic acid ester groups or maleic acid monoester groups.

By the above-described reaction of free hydroxyl groups with maleic anhydride and subsequent sulfonation with, for example

Sodium sulfide may be introduced into the sulfone succinate group by known methods. The residue T ^a then contains both a residue COO © Z © and a residue -S (O ₂ ) (OH) i. _y (O 0 Z ©) _y .

The introduction of a carboxymethyl group (T ^a = CH 2 COOH) can be carried out with the aid of sodium hydride and sodium chloroacetate.

Further methods for introducing a COOH or COO © Z-containing radical T ^a are the addition of a tert-butyl acrylate or acrylonitrile with subsequent hydrolysis and optionally salification.

By etherification of hydroxyl groups, which can also be carried out by methods which are known to those skilled in the art, it is possible to generate species for which s = t = 0. If the indices x and y are 0, free acids are present. However, it may be advantageous to convert these into salified by negatively charged groups. This is especially true when the pigments and / or fillers to be dispersed have a strong affinity for negatively charged adhesive groups.

The acidic hydrogen atoms of the different acid groups can be converted into the corresponding salts by reaction with a base.

Suitable salts are, for example, ammonium salts prepared by reacting one or more of the free acid groups with ammonium or a suitable organic amine, tertiary amines, preferably triethylamine, alkanolamines, such as, for example, triethanolamine, ammonium hydroxide or tetraalkylammonium hydroxide. Also suitable for the reaction with the acid groups alkali hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide or corresponding carbonates such as potassium carbonate or dicarbonates such as potassium dicarbonate. The polyethers of the formula (I) according to the invention preferably have at least one hydrophilic and at least one hydrophobic block, wherein in the presence of more than one hydrophilic and more than one hydrophobic block, the blocks are preferably arranged alternately. If branched structural units are to be introduced in the cationic polymerization with ring opening, the cationic polymerization with the aid of a starter molecule of the formula (III) or (VI) is preferably carried out with polymerization of oxetanes of the formula (VII) with R ⁵ = R ^5a to form a rather corresponding hydrophobic blocks, started, followed by a block of branched hydrophilic structures composed of oxetanes of the formula (VII) with R ⁵ = R ^5b . The polyethers of the formula (I) used according to the invention have in the radicals R ^5b and R ⁹ preferably 2 to 10, more preferably 2 to 8, most preferably 2 to 6 and most preferably 3 to 4 hydroxyl groups, of which 10 to 100 mol%, preferably 20% to 100 mol%, more preferably 30% to 100 mol%, of the above radicals -OP (O) (OH) ₂ -x (O © Z.sup.) _X , -O- S (O ₂₎ (OH) i _-y (O © © Z) y and / or -O- (C = O) _s - are (NH) _t -T ^a reacted. A

Reaction to the radicals -Ο-Ρ (Ο) (ΟΗ) 2 (Ο ^Θ Ζ ©) _χ is particularly preferred.

In a preferred embodiment of the species of formula (I) are 10 to 90 mol%, more preferably 20 to 80 mol%, most preferably 30 to 70 mol% of the hydroxyl groups in the radicals R ^5b and R ⁹ by a radical OT replaced.

Typical reaction conditions in the process according to the invention for the preparation of the polyethers of the formula (I) according to the invention or of the wetting and dispersing agents according to the invention

The monoalcohols used as starting units for the Oxetanpolymerisation can, as already mentioned above, also be selected from alkoxylated alcohols.

If glycidyl ethers, such as, for example, phenyl glycidyl ethers or glycidyl esters, are used as species of the formula (IV), then the ring-opening reaction can be carried out in detail, for example, as described in US Pat. No. 201 1/257326 A1.

The ring-opening polymerization of the oxetanes of the general formula (VII) to species of the general formula (III) or preferably (VI) is preferably carried out as a cationic oxetane ring-opening polymerization at about 30 ° C to 130 ° C, preferably at about 50 ° C to 1 10 ° C, in the presence of at least one catalyst. Preference is given to the oxetanes of the formula (VII) in which R ^{5 is} R ^5a or R ^5b or dosed their mixtures to the preheated reaction mixture, which is already at least one species of the general formulas (III) or preferably at least one of the species of the general formula ( VI) and at least one catalyst.

If a targeted buildup of hydrophobic and hydrophilic structural units in the oxetane-based part of the polyether of the general formula (I) is to be achieved, the corresponding hydrophilic or hydrophobic oxetanes of the formula (VII) are separated from one another and one after the other, optionally with a break between the different oxetanes. Monomers, metered.

Preferably, the synthesis of the polyethers of the formula (I) according to the invention by means of the cationic, ring-opening polymerization of the oxetanes of the formula (VII) by the selection of certain starting molecules of the formulas (III) or (VI) is facilitated.

As a rule, it is possible to carry out the reaction particularly well with starting molecules of the general formula (VI) where u = 0 and v> 2, preferably v> 6, particularly preferably v = 8 to 40. Particular preference is given to using alkyloxypolyalkylene oxides or aryloxypolyalkylene oxides. Preferred examples which may be mentioned are C 12 -alkoxy polyalkylene oxides, in particular C 12 -alkoxy poly (C 2-3 -alkylene oxides), for example methoxypolyethylene oxides. At the end of the reaction, the product is cooled and optionally the catalyst is neutralized by addition of a base. This can also be achieved with the aid of basic ion exchangers. For example, salts or solid catalysts may be removed from the reaction mixture by filtration. Suitable catalysts for the cationic ring-opening polymerization of oxetanes are, for example, Lewis acids, in particular AlCl 3, BF ₃ , TiCl ₄ , Zn, SiF ₄ , SbFs, PF 5, AsFs or SbCls and, for example, halogenated acids, in particular FSO 3 H, CISO 3 H, HCIO, HIO or CF3SO3H and other Brönsted Acids (such as p-toluenesulfonic acid and methanesulfonic acid) or heteropolyacids such as 12-tungstophosphoric or heteropolyacids, for example, the general compositions H ₄ XMi2O ₄ o with X = Si, Ge; M = W, Mo or H ₃ XMi ₂ O ₄ O and H ₆ X2Mi ₈ O62 with X = P, As; M = W, Mo suitable. In particular, catalytically active heteropolyacids may contain one or more moles of water of crystallization. As catalysts it is also possible to use onium salts, such as, for example, a sulfonium, an oxonium and / or iodonium salt. Examples of such compounds are benzyltetramethylenesulfonium hexafluoroantimonate, benzyltetramethylenesulfonium hexafluorophosphate and benzyltetramethylenesulfonium trifluoromethanesulphonate. The catalyst used is preferably 12-tungstophosphoric acid. Advantages of using this catalyst in the cationic polymerization of oxetanes are the relatively low reaction temperatures and the associated low thermal load of the product. However, it is particularly important to highlight the property of the catalyst, which does not affect the color of the products negatively, for example by browning or blackening. In addition, aromatic substituents in the monomers and in the product are not destroyed or chemically altered by the catalyst (saponification, substitution, electrophilic addition). Solvents can be used in the preparation of the polyethers of the formula (I) according to the invention. However, these must not influence the cationic oxetane ring-opening polymerization. Suitable solvents are, for example, those which contain no active hydrogen atoms, no polymerizable rings and no groups which react with the oxetanes of the formula (VII), in particular the hydroxyl groups of the hydroxyoxetanes (containing at least one radical R ^5b ), with the starting molecule of the formulas (III) or preferably of the formula (VI) or with intermediates or the resulting polyether of the formula (I). Preference is given to using aliphatic, cycloaliphatic and aromatic solvents, ketones and blocked polyethers as solvents.

The choice of solvent may also be based on the later intended use of the wetting and dispersing agents according to the invention. To be favoured low-boiling solvents are used to facilitate distilling off in those applications in which the polyethers of the formula (I) or the wetting and dispersing agents according to the invention to be used as 100% formulation, for example in radiation-curing, in particular UV-curing Compositions, in particular such coating compositions. The preparation of the target species preferably takes place in the presence of one or more solvents.

Use of the polyethers and the wetting and dispersing agents according to the invention in compositions according to the invention

The novel compositions comprise the above-defined polyethers of the general formula (I) according to the invention or the wetting and / or dispersing agents according to the invention, in particular for dispersing particulate solids, preferably pigments and / or

Fillers.

The compositions of the invention are preferably liquid at 25 ° C. The compositions according to the invention which are liquid at 25.degree. C. comprise the polyethers of the formula (I) according to the invention or the wetting agents and dispersants containing them or consisting thereof, preferably in amounts of 0.1 to 10% by weight, particularly preferably 0.3 to 8 Wt .-%, most preferably 0.5 to 5 wt .-% or 0.5 to 3 wt .-%, based on the total weight of the composition. If, in this context, a content of wetting and dispersing agents in the compositions according to the invention is mentioned, this content refers to the solvent-free wetting and dispersing agent, that is to say to the reaction product of the present invention

Process. The compositions according to the invention are preferably aqueous, solvent-free or solvent-containing coating formulations or millbases for their preparation or formulations for molding compositions, in particular SMC and BMC, which preferably contain dispersed pigments and / or fillers.

The compositions are suitable for numerous applications. For example, wetting and / or dispersing agents which are preferably used for the production of universal pastes, pigment surface modifications, color resists for color filters, pigment concentrates or compositions containing inorganic fillers such as in particular CaCO 3, BaSO ₄ or inorganic flame retardants such as aluminum oxide or aluminum trihydroxide (ATH) are required enable stable pigment and filler dispersions in different liquid media such as in organic solvents or in water and, accordingly, can also be further incorporated in aqueous media, solvent-free or solvent-containing media for further formulation. For example, a color resist during its processing is required to be readily soluble in an organic solvent such as methoxypropyl acetate and to rapidly dissolve in an alkaline aqueous solution which may contain surfactants. The corresponding compositions according to the invention have a direct influence on the properties of the end product.

This also applies to the production of pigmented paints, for the processing of which, despite high pigment loading, a low viscosity is required. In particular, a high viscosity reduction is required for highly filled plastic materials, so that they remain free-flowing and easy to process at maximum filler content. The compositions of the invention meet these and other requirements, so that they can be used for a variety of applications easily and with improved properties. This includes, for example, the complex phenomenon of the adhesion of coatings, which is the adhesion adhesion of coatings on an optionally pretreated substrate, in particular a metallic substrate, glass or plastics, the adhesion adhesion of coatings other coatings, in particular old paints, base coats and cathodic electrodeposition paints and the internal cohesive adhesion of a coating or plastic mass may include itself. By suitable choice of wetting and / or dispersing agent, in particular the cohesive adhesion and the adhesion adhesion can be positively influenced because the particle wetting improves, the mediation between organic matrix and pigments and fillers can be increased and separation effects can be specifically avoided.

Thus, the polyethers according to the invention or the wetting and / or dispersing agents according to the invention can be used, for example, in the production or processing of paints, printing inks, paper coatings, leather and textile dyes, pastes, pigment concentrates, ceramics or cosmetic preparations, if these pigments are solids and / or fillers. Also in the production or processing of casting and / or molding compositions based on synthetic, semi-synthetic or natural macromolecular substances, such as polyvinyl chloride, saturated or unsaturated polyester, polyurethanes, polystyrene, polyacrylates, polyamides, epoxy resins, polyolefins such as polyethylene or Polypropylene they can be used. For example, the compositions according to the invention containing dispersed pigments and / or fillers and optionally other additives can be used in casting compounds, PVC plastisols, gelcoats, polymer concrete, printed circuit boards, industrial coatings, wood and furniture coatings, vehicle finishes, marine paints, anticorrosive paints, can and Coil coatings, paints and building paints, if necessary spread very well after adding further binders. Examples of conventional further binders are resins based on polyurethanes, cellulose nitrates, cellulose losobutyrates, alkyd resins, melamine resins, polyesters, chlorinated rubbers, epoxy resins and polyacrylates. Examples of water-based coating formulations are cathodic or anodic electrodeposition paints, for example for automobile bodies. Other examples are plasters, silicate paints, emulsion paints, water-based paints based on water-dilutable alkyd resins, alkyd emulsions, hybrid systems, 2-component systems, polyurethane and acrylate resin dispersions.

The compositions of the invention are also particularly suitable as a basis for solid concentrates, such as pigment concentrates. For this purpose, the copolymers described above are initially charged in a dispersing medium, such as organic solvents, plasticizers and / or water, and the solids to be dispersed, preferably pigments and / or fillers, are added with stirring. In addition, further binders and / or other auxiliaries may be added to these compositions. Preferably, however, compositions which are free of binders other than the wetting and / or dispersing agents according to the invention already ensure stable pigment concentrates. It is likewise possible to use the compositions according to the invention as flowable solid concentrates. For this purpose, pigment presscakes, which may still contain organic solvents, plasticizers and / or water, are mixed with wetting and / or dispersing agents according to the invention and the mixture thus obtained is dispersed. The inventive prepared in various ways solid concentrates can then be divided into different compositions such. For example, alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins may be incorporated. However, pigments can also be dispersed directly in water or solvent-free manner with wetting agents and / or dispersants according to the invention. These compositions according to the invention are then particularly suitable for pigmenting thermoplastic and thermoset plastic formulations.

The compositions of the present invention may also be used to advantage in the preparation of inks for "non-impact" printing processes such as "thermal inkjet" and the "Bubblejef" process. These inks may be, for example, aqueous ink formulations, solvent-based ink formulations, solvent-free or low-solvent inks for UV applications, as well as waxy inks. The compositions according to the invention can also be used in the production of color filters for liquid crystal displays and liquid crystal displays, color resolvers, sensors, plasma screens, displays based on the SEDs (surface conduction electron emitter displays) and for MLCCs (multi-layer Ceramic compounds). Here, the liquid color filter varnish, which is also called Color Resist, can be applied by various application methods such as spin coating, knife coating, combination of both or by "non-impact" printing processes such as inkjet processes is used in the manufacture of microchips and printed circuit boards.

The compositions according to the invention can also be used in cosmetic preparations, for example in make-ups, powders, lipsticks, hair dyes, creams, nail varnishes and sunscreen preparations.

These may be in the usual forms. The preparations according to the invention containing the above-defined polyethers according to the invention as wetting and / or dispersing agents for pigments such as titanium dioxide or iron oxide and can be incorporated into the carrier media customary in cosmetics, such as, for example, US Pat

Water, castor oils or silicone oils are incorporated.

Another object of the present invention is the use of one or more of the polyethers according to the invention as or in wetting and / or dispersing agents for solids, more preferably for pigments and / or fillers or as a phase mediator. These pigment dispersions according to the invention containing compositions according to the invention can be used to produce a pigmented coating on a substrate, wherein the pigmented paint is applied to the substrate and baked thereon or cured or crosslinked. Another object of the present invention are therefore coating compositions, pastes and molding compositions containing the compositions of the invention or the polyethers of the invention or the wetting and / or dispersing agents of the invention and one or a plurality of dispersed pigments, organic solvents and / or water, and optionally other binders including customary coating auxiliaries

From the pigment dispersions according to the invention it is also possible to prepare pigment pastes according to the invention based thereon.

The compositions of the invention can be used alone or together with other conventional binders. When used in polyolefins, it may, for. B. be advantageous to add appropriate low molecular weight polyolefins as carrier materials to the inventive compositions.

Another object of the invention also relates to powdered particles and / or fiber-particulate solids, in particular of pigments or fillers such as plastic fillers, which are coated with polyethers according to the invention or wetting and / or dispersing agents according to the invention. These

Coating of organic or inorganic solids can be carried out in a known manner, as z. As described in EP-A-0 270 126. From the resulting compositions of the invention, the dispersing medium may either be removed or left to form pastes. In the case of pigments, this coating of the pigment surface can take place during or after the synthesis of the pigments, for example by adding the polyethers of the invention or the wetting and / or dispersing agents according to the invention to the pigment suspension or during or after the pigment finish. The compositions according to the invention obtained in this way are very suitable for incorporation as pretreated pigments or fillers and are distinguished by improved viscosity, flocculation and gloss behavior and by higher color strength compared with untreated pigments. Examples of pigments are mono-, di-, tri- and polyazo-pigments, oxazine, dioxazine, thiazine pigments, diketo-pyrrolo-pyrroles, phthalocyanines, ultramarine and other metal complex pigments, indigoid pigments, diphenylmethane, triarylmethane, xanthan , Acridine, quinacridone, methine pigments, anthraquinone, Pyranthrone, perylene and other polycyclic carbonyl pigments. Further examples of organic pigments can be found in the monograph: W. Herbst, K. Hunger "Industrial Organic Pigments", 1997 (Publisher: Wiley-VCH, ISBN: 3-527-28 836-8) Examples of inorganic pigments are pigments on Base of carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithophones, iron oxide, ultramarine, manganese phosphate, cobalt aluminate,

Cobalt stannate, cobalt zincate, antimony oxide, antimony sulfide, chromium oxide, zinc chromate, mixed metal oxides based on nickel, bismuth, vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum (for example nickel titanium yellow, bismuth titanium). vanadate molybdate yellow or chromium titanium yellow). Further examples are in the monograph: G. Buxbaum "Industrial Inorganic Pigments", 1998 (published by Wiley-VCH, ISBN: 3-527-28878-3) .Inorganic pigments can also be magnetic pigments based on pure iron, iron oxides and chromium oxides or mixed oxides, metallic effect pigments of aluminum, zinc, copper or brass as well as pearlescent pigments, fluorescent and phosphorescent luminescent pigments.

Further examples of particulate solids are nanoscale organic or inorganic solids having particle sizes below 100 nm, such as certain types of carbon black or particles consisting of a metal or semimetal oxide or hydroxide, as well as particles consisting of mixed metal and / or semimetal oxides or metal and / or Halbmetallhydroxiden exist. For example, the oxides and / or oxide hydroxides and / or hydroxides of aluminum, silicon, zinc, titanium, etc. may be used to produce such extremely fine particulate solids. The production process of these oxidic or hydroxidic or oxidic hydroxide particles can be carried out by a wide variety of processes, such as, for example, ion exchange processes, plasma processes, sol-gel processes, precipitation, comminution (for example by grinding) or flame hydrolysis. These nanoscale solids can also be so-called hybrid particles, which consist of an inorganic core and an organic shell - or vice versa. Examples of pulverulent or fibrous fillers are, for example, those which are composed of pulverulent or fibrous particles of aluminum oxide, aluminum hydroxide, silicon dioxide, diatomaceous earth, silica, quartz, silica gel, talc, kaolin, mica, perlite, feldspar, slate meal, calcium sulfate, Barium sulfate, calcium carbonate, calcite, dolomite, glass or carbon. Further examples of pigments or fillers are found, for example, in EP-A-0 270 126. Flame retardants such as, for example, aluminum or magnesium hydroxide and matting agents such as, for example, silicic acids can also be excellently dispersed and stabilized.

The invention likewise relates to the use of the wetting and dispersing agents according to the invention in so-called sheet-molding compounds (SMC) and bulk-molding compounds (BMC), which consist of fiber-reinforced and filler-containing reactive resins which are under pressure in a hot mold to be cured to a molding. As fibers in addition to glass fibers and carbon fibers, basalt fibers and natural fibers and other reinforcing fibers, used as loose fiber shreds, directed continuous fibers, fiber mats, -layed, - knitted, in one or more layers use. Use, as resin components include unsaturated polyesters, vinyl esters or epoxy resins, which can also be used with other resin components in Hybridsytemen. Many of the formulations contain fillers such as chalk, clay, barium sulfate, aluminum trihydroxide or magnesium hydroxide, which are used separately or in mixtures.

The preparation and processing of such molding compositions is exemplified by the example of the unsaturated polyester in DE3643007 and in the monograph of P.F. Bruins, "Unsaturated Polyester Technology", Gordon and Breach Science Publishers 1976, pages 211 to 238.

The increase in fiber and filler content often serve to increase the stiffness and improve the surface quality. The resulting increase Viscosity of the resin / filler mixtures is so high that in conventional systems the surface wetting of the reinforcing fibers is no longer complete and proper, the deaeration of the mixture is degraded and even the pot life of the system can be shortened. In such cases, this leads to a qualitative deterioration of the mechanical properties such as the tensile or bending strength of the final molding.

The use of the wetting and dispersing agents according to the invention results in a significant reduction in the viscosity of the resin-filler mixtures, so that perfect fiber wetting and impregnation is ensured even in the case of formulations with a high filler content.

Thus, by using the wetting and dispersing agents according to the invention, it is likewise possible to increase the amount of flame retardants which can be used, for example aluminum trihydroxide or magnesium hydroxide, to such an extent that a significant improvement in the flame-retardant properties in the cured molded part is possible. This leads to a classification of such components in a higher-grade fire protection class, measurable, for example, according to the UL 94 method of Underwriters Laboratories (according to DIN EN 60695-1 1 -10) or according to other, typically used in transport methods (see, for example, "Fire behavior of building materials and components ", DIN 4102), thus enabling new, further areas of application for such SMC and BMC molded parts.

EXAMPLES Abbreviations

MeOH = methanol

BuOH = n-butanol

MPG = phenoxyethanol

MPEG 500 = methoxypoly (ethylene glycol) (number average molecular weight M _n = 500 g / mol)

Ethylene oxide = EO

Propylene oxide = PO

Phenyl glycidyl ether = PhGE 2-ethylhexyl glycidyl ether = 2-EHGE

3-Ethyl-3 - ((phenoxy) methyl) oxetane = PhOx

3-ethyl-3 - ((2-ethylhexyloxy) methyl) oxetane = 2-EHOx

3-ethyl-3- (hydroxymethyl) oxetane = TMPOx

3-Ethyl-3- (polytri (oxyethylene) hydroxymethyl) oxetane = 3EO-TMPOx

To study the rate of reaction of the ring-opening oxetane polymerization under the conditions described below, online IR measurements were performed on an ABB MB-Rx instrument equipped with an ATR rod probe with diamond crystal. It was found that no monomer accumulation occurs under the selected reaction conditions. The monomer signals present during the metering, which have been assigned to the oxetane function, disappear under the chosen reaction conditions within a few minutes, which is why then a complete monomer conversion may be assumed. Corresponding titrimetic measurements of the oxetane number confirmed the complete reaction of the oxetane monomers.

The following measuring methods were used to characterize the polyethers according to the invention:

Titration of oxetane groups for end point determination

Approximately 0.03 to 0.04 grams of the sample were accurately weighed into an 80 ml beaker and dissolved in 10 ml of chloroform and 40 ml of concentrated acetic acid. The sample was heated to 50 ° C (15 minutes in the thermoblock). After addition of 2.5 g of cetyltrimethylammonium bromide, the sample was placed on the magnetic stirrer, the electrode immersed well and titrated hot with 0.1 N acetic perchloric acid. With an equivalent weight of> 30,000, the reaction is considered complete.

Oxetane equivalent = weight (g) ^* 1000 / (consumption (ml) ^* n ^* f)

n = normality of the titrant

f = factor of the titrant Gel permeation chromatography (GPC)

Gel permeation chromatography was performed at 40 ° C using a high pressure liquid chromatography pump (Bishoff HPLC 2200) under a Refractive Index Detector (Waters 410). The eluent was tetrahydrofuran at a flow rate of 1 mm / min. Using polystyrene standards, a conventional calibration was achieved. The number-average molecular weight Mn, the weight-average molecular weight Mw and the polydispersity PD = Mw / Mn were calculated according to FIG. calculated by the program NTeqGPC.

NMR measurement

The NMR measurements were carried out on a Bruker DPX 300 at 300 MHz ( ¹ H) and 75 MHz ( ¹³ C), respectively. The solvent used was deuterated chloroform (CDCl 3) and deuterated dimethyl sulfoxide (DMSO cfe).

In the following sections, the preparation of the polyether used according to the invention is explained by corresponding methods. An overview of the structural variations of the polyethers of Examples 1 to 8 according to the invention and Examples 9 * and 10 * not according to the invention can be taken from Table 1.

Table 1

^* Comparative Examples (contain no aromatic residues on the polyether backbone); Comparative Example 10 ^* is based on Example R of US 8,258,189 B2

Monohydroxy component X1

To prepare the monohydroxy-functional starting alcohol X1 are in a 250 ml 4-necked flask equipped with stirrer, condenser, thermometer and dropping funnel 0.1 mol Lutensol ON 1 10, (C10-oxo alcohol started monohydroxyfunktioneller EO polyether, Mn 625 g / mol from BASF) at 40 ° C. with 30 mg of ionol CP while passing over nitrogen with a solution of potassium tert-butoxide (KOtBu) in THF (1 mol / L). The amount of KOtBu with a slight stoichiometric excess of 1.05: 1 is used for the amount of substance of the polyether or of the lutensol. The resulting tert-butanol is removed within 60 min stirring in vacuo (50 mbar), wherein the reaction temperature is raised to 120 ° C within this time. Then, slowly (within 2 h), 0.2 moles of PhGE are added dropwise via a dropping funnel. The reaction mixture may turn from pale yellowish to reddish / brownish during the experiment. After completion of the metering is stirred at 120 ° C for 2h. The catalyst residues can be removed by adding 5 ml of water at 60 ° C. and then adding 3% by weight (based on the batch size) of magnesium silicate (Florisil Absorbent, available from ChemPure Chemicals, CAS 1343-88-0). After 60 min stirring at 60 ° C and under nitrogen atmosphere, the mixture is filtered.

Synthesis Example S1 - "Linear Polyether (Example 1)"

To prepare the dispersant, 50.0 g (0.1 mol) of MPEG 500 (methanol-started monohydroxy-functional EO polyether, Mn 500 g / mol from Clariant) were introduced into a 250 ml 4-necked flask equipped with stirrer, condenser, thermometer and dropping funnel. with 30 mg of ionol CP heated to 85 ° C with the transfer of nitrogen. After 20 minutes, 120 mg of PW12 (Phosphotungstic acid hydrates, Sigma Aldrich P4006, CAS 12501 -23-4) are added to the mixture. 57.6 g (0.3 mol) of PhOx were then added dropwise very slowly (within 4 h) via a dropping funnel. The reaction mixture remained colorless to pale yellow during the experiment. After 2 h post-reaction time, the mixture was cooled and neutralized with sodium bicarbonate. The mixture was then filtered. Synthesis Example S2 - "linear random polyether (Example 2)"

To prepare the dispersant, 50.0 g (0.1 mol) of MPEG 500 (methanol-started monohydroxy-functional EO polyether, Mn 500 g / mol from Clariant) were introduced into a 250 ml 4-necked flask equipped with stirrer, condenser, thermometer and dropping funnel. with 30 mg of ionol CP heated to 85 ° C with the transfer of nitrogen. After 20 minutes, 120 mg of PW12 (Phosphotungstic acid hydrates, Sigma Aldrich P4006, CAS 12501 -23-4) are added to the mixture. Subsequently, a mixture of 38.1 g (0.2 mol) of PhOx and 22.8 g (0.1 mol) of 2-EHOx was added dropwise very slowly (within 4 h) via a dropping funnel. The reaction mixture remained colorless to pale yellow during the experiment. After 2 h postreaction time, the

Cooled mixture and neutralized with sodium bicarbonate. The mixture was then filtered.

APPLICATIONS

In the following application examples, the use of the dispersants used according to the invention in comparison with dispersants which can not be used according to the invention were tested as additives in pigment pastes or in corresponding paints.

Abbreviations and raw materials: Acticide MBS biocide, manufacturer Thor GmbH

Hellogengreen L 8730 pigment, manufacturer BASF SE

Flammruß 101 pigment, manufacturer Degussa

DMEA dimethylethanolamine

BYK-1730 defoamer, manufacturer BYK-Chemie GmbH Application of the oxetane copolymers according to the invention as wetting and dispersing additives for universal pigment concentrates

First, aqueous, pigment abrasions A1 to A3 * (black) and B1 to B3 * (green) were prepared and these were assessed for viscosity, foaming and sediment. In addition, paints were formulated based on these anhydrides, whereby a pigmented clear coat was prepared for evaluation of gloss in the elevator on contrast cards and two white blends for assessing color paste uptake and pigment stabilization by means of rubout.

Formulation of the pigment concentrates A1 to A3 * based on flame black 101 with 40% by weight of additive (sop) To produce the pigment concentrates A1 to A3 *, the stated raw materials, additives and the pigment were weighed successively into a disperse pot. Subsequently, 1 mm glass beads 1: 1 in parts by weight were added and the mixture for 60 min at 21 m / s dispersed in a Dispermat CV. The pH was adjusted to pH 8 with DMAE. Subsequently, the quality of the dispersion was assessed visually, whereby homogeneity, thixotropy, foam and sediment were assessed. The same assessment was also made after aging overnight at room temperature. For the formulation A3 *, which contains the non-inventive polymer 10 *, no stable pigment concentrate was obtained.

Pigmentation without

A1 A2 A3 * additional binders

Additive (wt.%) 3 1 10 *

Water 71, 0 71, 0 71, 0

Additive (as 100%

8.0 8.0 8.0 active substance)

BYK-1730 1, 0 1, 0 1, 0

Acticide MBS 0.1 0.1 0.1

Flammruß 101 19.9 19.9 19.9

Assessment of pigment concentrates

After sedimentation no sediment no sediment sediment fluidly slightly stocky - no foam no foam slightly foamy homogeneous homogeneously inhomogeneous

After 1 day at 25 ° C no sediment no sediment - thin slightly thixotropic - homogeneous homogeneous -

Formulation of the pigment concentrates B0 * to B3 based on Heliogen green L8730 with 15% by weight of additive (sop) To prepare the pigment concentrates B1 to B3 *, the specified raw materials, additives and the pigment were weighed successively into a glass bottle. Subsequently, 1 mm glass beads 1: 1 in parts by weight were added and the mixture for 2 h in a Lau Shaker at 40 ° C dispersed. The pH was adjusted to pH 8 with DMAE. Subsequently, the quality of the dispersion was visually evaluated, whereby homogeneity, thixotropy, foam and sediment were evaluated. The same assessment was also made after aging overnight at room temperature. For the formulation B3 *, which contains the non-inventive polymer 9 *, no stable pigment concentrate was obtained. Pigmentation without

B1 B2 B3 * additional binders

Additive (% by weight) 3 1 9 *

Water 52.4 52.4 52.4

Additive (as 100% active substance) 6.0 6.0 6.0

BYK-1730 1, 0 1, 0 1, 0

Acticide MBS 0.1 0.1 0.1

Heliogen green L 8730 40.0 40.0 40.0

Assessment of pigment concentrates

After sedimentation no sediment no sediment sediment homogeneously homogeneous inhomogeneous

After 1 day at 25 ° C no sediment no sediment - homogeneous homogeneous -

For the determination of the alcohol compatibility, blends of the pigment concentrates A1 and A2 were prepared in the following white-pigmented alkyd lacquers. Pigment concentrate A3 * could not be used due to the poor quality of the pigmented finish.

To determine the alkyd compatibility, blends of the pigment concentrates B1 and B2 were prepared in the following white-pigmented alkyd lacquers. Pigment concentrate B3 * was already unusable due to the poor quality of the pigment preparation.

1 varnish 130 B30 Alkyd-based high-gloss varnish-free varnish; Brillux

2 Rubbol AZ, long-oil, solvent-based alkyd resin paint, manufacturer Sikkens

3 Impredur 840 Solvent-based glossy lacquer based on alkyd resin; Brillux In each case, 97 parts of the white-pigmented alkyd paint were weighed into glass surfaces with 3 parts of the respective pigment concentrate A1 and A2 or B1 and B2 and shaken for 5 min at 40 ° C in the Lau Shaker for homogenization.

All white blends of the formulations according to the invention tend to have relatively high a and b values, which indicates a good stabilization of the flame black. In addition, the ΔΕ values for rubout for the formulations according to the invention are very low and thus correspond to the requirements. Pigment concentrate B1 B2

Alkyd compatibility Buntlack 130 B30, mixing ratio: 97: 3

elevator

L ^* 67.15 67.74 a ^* -46.86 -44.64 b ^* 3.73 3.74

rubout

L ^* 67.62 67.64 a ^* -48.02 -46.81 b ^* 3.23 3.02

Rubout to elevator

ΔΕ 1, 33 2.27

Pigment concentrate B1 B2

Alkyd Compatibility Rubbol AZ, Blend Ratio: 97: 3

elevator

L ^* 71, 92 72.12 a ^* -42.37 -41, 68 b ^* 1, 39 1, 43

rubout

L ^* 72.15 72.07 a ^* -43.62 -43.41 b ^* 0.67 0.78

Rubout to elevator

ΔΕ 1, 45 1, 84

Pigment concentrate B1 B2

Alkyd Compatibility in Impredur 840 White, Mise Ratio: 97: 3

elevator

L ^* 73.12 73.29 a ^* -39.67 -38.97 b ^* 1, 1 1 1, 2

L ^* 73.22 73.61 a ^* -41, 65 -40.93 b ^* 0.45 0.41

Rubout to elevator

ΔΕ 2.08 2.13 The white blends of formulations B1 of the invention tend to have smaller a values, indicating a stronger green. However, all of the white blends of the formulations B1 and B2 according to the invention show lower ΔΕ values during rubbing and thus correspond to the requirements.

Claims

claims

1 . Polyethers of the general formula (I):

(I)

wherein

u stands for 0 or 1

vv stands for 1 to 60,

w is 1 to 20,

R ^{1 is} a monovalent organic radical having from 1 to 10 carbon atoms, R ^{2 is} a divalent organic radical, and

when u = 0 is CHR ^2a CHR ^2b , where

R ^2a and R ^2b are each independently

Hydrogen, or

monovalent organic radicals selected from the group consisting of

aliphatic radicals having 1 to 8 carbon atoms,

aromatic radicals having 6 to 8 carbon atoms, or araliphatic radicals having 7 to 10 carbon atoms; and the

when u = 1 is an aliphatic radical having 2 to 24 carbon atoms;

R ³ , R ⁴ , R ⁷ and R ⁸ are each independently

Hydrogen, or

monovalent organic radicals are and are selected from the group consisting of

aliphatic radicals having 1 to 8 carbon atoms,

aromatic radicals having 6 to 8 carbon atoms, or araliphatic radicals having 7 to 10 carbon atoms,

R ^{5 is} a radical R ^5a or R ^5b , and

R ^5a for

is a monovalent organic radical and is selected from the group consisting of

aliphatic radicals having 1 to 20 carbon atoms,

aromatic radicals having 6 to 12 carbon atoms,

araliphatic radicals having 7 to 24 carbon atoms,

R ^5b for

a radical CH 2 -OR ^5c , wherein R ^{5c is}

Hydrogen or

aliphatic radicals having 1 to 24 carbon atoms,

aromatic radicals having 6 to 14 carbon atoms, and araliphatic radicals having 7 to 18 carbon atoms,

R ^{6 is} hydrogen or a radical R ^5a

R ⁹ is defined as R ^5c and is independently selected from R ^5c ; and

in which

(A) the radicals R ¹ , R ² , R ³ , R ⁴ , R ^5a , R ⁶ , R ⁷ and R ^{8 are} free of carboxy, hydroxy, thiol, imino and primary and secondary amino groups, (b ) at least one, preferably 2 to 6, particularly preferably 2 to 4 of the radicals R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ contained in formula (I) are aromatic or araliphatic radicals or an aromatic or araliphatic radical, and (c) 0 to 100 mol%, via the above radicals R ^5b and R ⁹ and / or by

Cleavage of hydrolytically cleavable radicals resulting hydroxyl groups are replaced by radicals OT, which are selected from the group consisting of Radicals -Ο-Ρ (Ο) (ΟΗ) _2-χ (Ο © Ζ ©) χ, where x is 0, 1 or 2,

Residues -O- (C = O) _s - (NH) _t -T ^a wherein s is 0 or 1 and t is 0 or 1, and in the case that s = 0, and t = 0, and wherein T ^{a is} a monovalent organic radical having 1 to 100 carbon atoms, optionally one or more of the following radicals

COOH,

COO © Z ®,

-OS (O ₂ ) (OH) i _-y (O © Z ©) _y , and the above Z z are independently of each other alkali metal cations, an ammonium ion or protonated or quaternized amines.

A polyether according to claim 1, wherein

u is 0 or 1,

v stands for 2 to 45,

R ^{1 is} a monovalent organic radical having 1 to 50 carbon atoms,

u stands for 0 or 1

R ² when u = 0 is CHR ^2a CHR ^2b where

one of the radicals R ^2a and R ^2b for

Is hydrogen and the other radical is hydrogen or an aliphatic radical having 1 to 4 carbon atoms or a radical CH ₂ -O-phenyl; and the

when u = 1, R ^{2 is} an aliphatic radical having 4 to 6 carbon atoms;

R ³ , R ⁴ , R ⁷ and R ⁸

represent hydrogen;

R ^{5 is} a radical R ^5a or R ^5b , and

R ^{5a is} a CH ₂ -OR ^5d radical, wherein R ^{5d is} a linear alkyl group having 2 to 10 carbon atoms, a branched or cyclic alkyl group 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms or an alkylaryl group having 7 to 14 carbon atoms, and

R ^{5b is} a radical CH ₂ -OR ^5c , wherein R ^{5c is}

Hydrogen or

aliphatic radicals having 1 to 24 carbon atoms;

R ^{6 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms

stands;

R ⁹ is defined as R ^5c and is independently selected from R ^5c ; and where

0 to 100 mol%, which are replaced by the above radicals R ^5b and R ⁹ or by elimination of hydrolytically cleavable radicals resulting hydroxyl groups by radicals OT, which are exclusively selected from the group consisting of

Rests -Ο-Ρ (Ο) (ΟΗ) ₂ -χ (Ο ^Θ Ζ ©) _χ , wherein x is 0, 1 or 2 and the cations Z © independently represent alkali metal cations, an ammonium ion or protonated or quaternized amines.

3. wetting and / or dispersing agent containing or consisting of polyethers of the formula (I) as defined in claims 1 and 2.

4. A process for the preparation of the polyethers of claims 1 or 2 or the wetting and / or dispersing agents of claim 3, wherein one or more mono-alcohols of the general formula (III)

R ¹ -OH (III) with one or more species of the general formulas (IV), (V) and (Vb)

ring-opening reaction or one or more of the species of general formula (Vb)

be converted in a condensation reaction to species of general formula (VI):

when using one or more of the species of the general formula (IV) u = 0 and when using one or more species of the general formulas (V), (Va) or (Vb) u = 1, and wherein the species of the general Formula (VI) with one or more species of the general formula (VII)

be reacted under ring opening reaction, and

0 to 100 mol%, preferably 0 mol%, of the hydroxyl groups formed via the radicals R ⁵ and R ⁹ and / or by removal of hydrolytically removable radicals

(i) by phosphorylation and in the case of x = 1 or 2 by subsequent salification in radicals -Ο-Ρ (Ο) (ΟΗ) 2 (Ο ^Θ Ζ ©) _χ implemented, and / or

(ii) by sulfonylation in the case of y = 1 by subsequent salification in radicals -OS (O2) (OH) i _-y (O ® Z ©) y reacted, and / or

(iii) reacted with di- or polycarboxylic acids, their anhydrides or halides, whereby the radical T ^{a contains} one or more COOH radicals which are optionally converted by salification into COO © Z © radicals,

(iv) are reacted with one or more of the species of formulas (IV), (V), (Va) and (Vb) and then optionally subjected to phosphorylation (i) and / or sulfonylation (ii) or reaction (iii) be, and / or

(V) by addition reaction with monoisocyanates of the formula T ^a -NCO in radicals -O- (C = O) _s - (NH) tT ^a , wherein s = t = 1, are reacted, and

in which

the radicals R ¹ , R ² , R ^2a , R ^2b , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , T ^a and Z © and the indices u, v and x, y as in claims 1 and 2 are defined and at least one of R ² , R ^2a , R ^2b , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 is} an aromatic or araliphatic radical or contains an aromatic or araliphatic radical.

5. The method of claim 4, wherein a. the species of the formula (VII) used are exclusively those in which all R ⁵ radicals are R ^5a or in which all R ^5b radicals are R ^5b ; or where

b. the species of formula (VII) employed is a mixture of species of residues R ^5a and species of residues R ^5b ; and

R ^5a and R ^{5b are} as defined in claim 1 or 2.

6. The method of claim 5, wherein the radical R ^{5b contains} one or more hydroxyl groups and / or one or more ether oxygen atoms.

7. A process according to claim 6, wherein the radical R ^5b contains a plurality of ether oxygen atoms linked by 2 or 3 carbon atoms in the shortest chain to another ether oxygen atom or a hydroxyl group, and hydroxyl groups optionally partially or completely contained in one or more of the reactions (i) , (ii), (iii), (iv) and (v) have been subjected according to claim 4.

8. Use of one or more of the polyethers of general formula (I) according to any one of claims 1 or 2 or one or more of the reaction products according to any one of claims 4 to 7 as wetting and dispersing agent for particulate solids in compositions containing them ,

9. Use according to claim 8, wherein the particulate solids are pigments and / or fillers.

10. A composition comprising one or more of the polyethers of the general formula (I) according to one of claims 1 or 2; or containing one or more wetting and / or dispersing agents according to claim 3; or containing one or more reaction products obtainable by a process according to any one of claims 4 to 7; as well as pigments and / or fillers.

1 1. A composition according to claim 1 1, wherein the composition is liquid at 25 ° C.

12. The composition according to any one of claims 10 or 11, wherein the composition is a coating agent, a molding material, a paste, an ink or a cosmetic. 13. A composition according to any one of claims 10 to 12, wherein the

A polyether of formula (I), the wetting and dispersing agent or the reaction product according to any one of the methods of claims 4 to 7 in an amount of 0.1 to 10 wt .-% based on the total weight of the composition. 14. A composition according to any one of claims 10 to 13 wherein the composition is a sheet-molding compound or a bulk-molding compound.

15. A composition according to any one of claims 10 to 14, wherein the composition comprises one or more fillers selected from the group consisting of aluminum trihydroxide, chalk, clay, barium sulfate, and magnesium hydroxide.