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WO2018091448A1 - Polyéther à base d'oxétanes pour utilisation en tant qu'agents mouillants et dispersants, et leur utilisation - Google Patents

Polyéther à base d'oxétanes pour utilisation en tant qu'agents mouillants et dispersants, et leur utilisation Download PDF

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Publication number
WO2018091448A1
WO2018091448A1 PCT/EP2017/079159 EP2017079159W WO2018091448A1 WO 2018091448 A1 WO2018091448 A1 WO 2018091448A1 EP 2017079159 W EP2017079159 W EP 2017079159W WO 2018091448 A1 WO2018091448 A1 WO 2018091448A1
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radicals
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Inventor
Michael Bessel
Guillaume Wojciech JAUNKY
Frederik Piestert
Carsten Nagel
Sandra Sabrina MEYER
Dennis LEVERING
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BYK Chemie GmbH
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BYK Chemie GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/328—Polymers modified by chemical after-treatment with inorganic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
    • C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
    • C08G65/3355—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus having phosphorus bound to carbon and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • 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.
  • wetting agents and / or dispersants are needed as auxiliaries. For this, they have to fulfill two different functions.
  • dispersants should therefore usually have hydrophobic radicals, such as, for example, relatively long-chain alkyl radicals or aryl radicals.
  • hydrophobic radicals such as, for example, relatively long-chain alkyl radicals or aryl radicals.
  • aqueous dispersing media the dispersants water-soluble, hydrophilic radicals, such as, for example, salified carboxylic acids.
  • polymeric dispersants which can optionally be subsequently modified by a polymer-analogous reaction, for example in the side chains.
  • the monomers in the polymer chain are incorporated randomly or alternately, in a gradient-like or block-like manner.
  • 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.
  • 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.
  • 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
  • GTP Group Transfer Polymerization
  • NMP Nitroxyl Mediated Polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer Process
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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
  • R 2a and R 2b are each independently
  • R 3 , R 4 , R 7 and R 8 are each independently
  • monovalent organic radicals are and are selected from the group consisting of
  • R 5 is a radical R 5a or R 5b , and R 5a for
  • R 6 is hydrogen or a radical R 5a
  • R 9 is defined as R 5c and is independently selected from R 5c ;
  • 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
  • Residues OT are replaced, which are selected from the group consisting of Radicals - ⁇ - ⁇ ( ⁇ ) ( ⁇ ) 2 - ⁇ ( ⁇ ⁇ ⁇ ⁇ ) ⁇ , where x is 0, 1 or 2,
  • radicals Z® independently of one another represent alkali metal cations, an ammonium ion or protonated or quaternized amines.
  • organic radical as used herein means an aliphatic, aromatic or araliphatic radical.
  • aliphatic radical 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.
  • aliphatic radical thus also includes the cycloaliphatic radicals (also referred to as alicyclic radicals).
  • 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.
  • an aliphatic radical may also contain heteroatoms, which in the latter case is a so-called heteroaliphatic radical.
  • 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
  • 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.
  • aliphatic radical means an aliphatic radical substituted with one or more aromatic radicals.
  • hydrocarbyl radical 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.
  • heteroatoms for example ether oxygen atoms
  • heteroatom group-containing radicals for example, hydroxyl groups
  • 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.
  • the radicals mentioned satisfy the above conditions they may by definition also contain heteroatoms such as, for example, polyoxazoline radicals.
  • 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 .
  • 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.
  • 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.
  • a methylphenyl radical is an aromatic radical of 7 carbon atoms.
  • 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
  • benzyl radical is for example a Araliphatic residue with 7 carbon atoms.
  • 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.
  • a p-methylbenzyl radical is an araliphatic radical of 8 carbon atoms.
  • 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.
  • R 2 is a bivalent organic radical of the formula CHR 2a CHR 2b .
  • R 2a and R 2b are a bivalent organic radical of the formula CHR 2a CHR 2b .
  • at least one of R 2a and R 2b is
  • the radical CHR 2a CHR 2b is an ethylene radical CH 2 CH 2 .
  • 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.
  • R 2a and R 2b are 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.
  • Other heteroatoms, in particular nitrogen atoms, are preferably not contained in these radicals.
  • ether oxygen atoms or carboxylic acid ester groups 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.
  • radicals R 2a or R 2b are those having exactly one ether oxygen atom or exactly one carboxylic acid ester group
  • 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.
  • hydrocarbon radical R 2c is an aromatic radical, it preferably contains 6 to 14, particularly preferably 6 to 12 or very particularly preferably
  • hydrocarbon radical R 2c is an araliphatic radical, it preferably contains 7 to 16, particularly preferably 7 to 12 or very particularly preferably
  • 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.
  • 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.
  • the radicals R 3 , R 4 , 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 is 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 radical R 5 is a radical R 5a or R 5b .
  • 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.
  • R 5a an ether oxygen atom
  • this is preferably a radical -CH 2 OR 5d, 5d
  • 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.
  • radical 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.
  • radical R 5b is a monovalent, one or more hydroxyl groups and one or more ethers containing oxygen
  • Species suitable for this purpose are listed below under the general formulas (IV), (V), (Va), (Vb) and (VII).
  • 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.
  • 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 ** -
  • 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):
  • 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.
  • 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 ,
  • R 6 is preferably defined as R 5a or it is hydrogen.
  • 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.
  • 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.
  • -OS (O 2) contains (OH) i -y (O ⁇ 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.
  • 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.
  • 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.
  • 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%"
  • the limits "10 to 100 mol%", "20% to 100 mol%", and "30% to 100 mol%”
  • species (i) and (ii) which in total also realizes the lower limit of 10 mol%.
  • 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.
  • 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.
  • R 1 is a branched or unbranched alkyl radical having 1 to 20, more preferably 1 to 16 or 1 to 12 carbon atoms,
  • 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 ⁇ ( ⁇ ) ( ⁇ ) 2 ( ⁇ ⁇ ⁇ ⁇ ) ⁇ are replaced, and wherein x and Z + are as defined above.
  • hydroxyl groups formed via the above R 5b and R 9 radicals or by elimination of hydrolytically removable radicals are present as hydroxyl groups.
  • 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.
  • 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.
  • wetting and / or dispersing agents are prepared as set out in the following section.
  • these wetting and dispersing agents consist of
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • R 2a and R 2b are each hydrogen, the units [OR 2 ] are ethylene oxide units.
  • 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
  • the adducts of (III) and (IV) used as starting units for the Oxetanpolymerisation can also be selected from alkoxylated alcohols.
  • alkoxy-Herten monoalcohols for example, available under the trade name Luten sol® from BASF SE, Ludwigshafen
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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):
  • one or more oxetanes of the formula (VII) can be added to the species of the formula (VI):
  • 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.
  • radicals R 3 , R 4 , R 7 and R 8 are methyl or hydrogen, most preferably hydrogen.
  • 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.
  • 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.
  • 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%.
  • R 5 is a radical R 5b and R 6 is R 5a .
  • 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.
  • 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.
  • a random, blocky or gradient-like structure can be used within the remainder
  • 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.
  • 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.
  • 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.
  • groups OT as described below.
  • R 2a and R 2b will be hydrogen. That is, the polyoxetane portion (s) are introduced through hydrophilic polyethylene oxide portions.
  • 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.
  • 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
  • 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.
  • residues - ⁇ - ⁇ ( ⁇ ) ( ⁇ ) 2 ( ⁇ ⁇ ⁇ ⁇ ) ⁇ can be introduced for example by a total or partial phosphorylation of the hydroxyl groups with polyphosphoric acid, polyphosphoric acids or phosphoric acid chlorides.
  • 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.
  • 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.
  • 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.
  • free hydroxyl groups can be completely or partially esterified with acetic acid, in which case T a is a methyl group.
  • radicals T a can be introduced which contain a COO ⁇ Z® radical.
  • Particularly suitable polycarboxylic acids or their anhydrides are cyclic carboxylic acid anhydrides, such as maleic anhydride, succinic anhydride and trimellitic anhydride.
  • 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.
  • 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 .
  • T a CH 2 COOH
  • 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.
  • 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.
  • 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
  • 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.
  • the monoalcohols used as starting units for the Oxetanpolymerisation can, as already mentioned above, also be selected from alkoxylated alcohols.
  • 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.
  • 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.
  • 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.
  • catalytically active heteropolyacids may contain one or more moles of water of crystallization.
  • onium salts such as, for example, a sulfonium, an oxonium and / or iodonium salt.
  • 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.
  • 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).
  • solvent may also be based on the later intended use of the wetting and dispersing agents according to the invention.
  • 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.
  • 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
  • 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
  • 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.
  • compositions are suitable for numerous applications.
  • 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.
  • inorganic fillers such as in particular CaCO 3
  • BaSO 4 or inorganic flame retardants such as aluminum oxide or aluminum trihydroxide (ATH)
  • 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.
  • organic solvent such as methoxypropyl acetate
  • 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.
  • 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.
  • the adhesion 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
  • the internal cohesive adhesion of a coating or plastic mass may include itself.
  • 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
  • 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.
  • 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.
  • 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.
  • further binders are resins based on polyurethanes, cellulose nitrates, cellulose losobutyrates, alkyd resins, melamine resins, polyesters, chlorinated rubbers, epoxy resins and polyacrylates.
  • 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.
  • compositions of the invention are also particularly suitable as a basis for solid concentrates, such as pigment concentrates.
  • 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.
  • a dispersing medium such as organic solvents, plasticizers and / or water
  • further binders and / or other auxiliaries may be added to these compositions.
  • 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.
  • 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.
  • inventive prepared in various ways solid concentrates can then be divided into different compositions such.
  • alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins may be incorporated.
  • 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.
  • 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).
  • liquid color filter varnish which is also called Color Resist
  • 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.
  • 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.
  • compositions 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 can be incorporated into the carrier media customary in cosmetics, such as, for example, US Pat
  • 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.
  • 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
  • compositions of the invention can be used alone or together with other conventional binders.
  • 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.
  • 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.
  • 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.
  • organic pigments can be found in the monograph: W. Herbst, K.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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.
  • nanoscale solids can also be so-called hybrid particles, which consist of an inorganic core and an organic shell - or vice versa.
  • 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.
  • 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.
  • SMC sheet-molding compounds
  • BMC bulk-molding compounds
  • 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.
  • 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 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.
  • 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.
  • 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.
  • Oxetane equivalent weight (g) * 1000 / (consumption (ml) * n * f)
  • n normality of the titrant
  • 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).
  • Comparative Examples (contain no aromatic residues on the polyether backbone); Comparative Example 10 * is based on Example R of US 8,258,189 B2
  • 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.
  • aqueous, pigment abrasions A1 to A3 * (black) and B1 to B3 * (green) were prepared and these were assessed for viscosity, foaming and sediment.
  • 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 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
  • 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.
  • 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.
  • Impredur 840 Solvent-based glossy lacquer based on alkyd resin; Brillux
  • 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.
  • 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 ⁇ values during rubbing and thus correspond to the requirements.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne des polyéthers de formule générale (I) dans laquelle les radicaux R1, R2, R3, R4, R5a (comme cas particulier du radical R5), R6, R7 et R8 sont dépourvus de groupes carboxy, hydroxy, thiol, imino et de groupes amino primaires et secondaires, les radicaux R5b (comme cas particulier du groupe R5) et R9 contiennent des groupes hydroxyle, pouvant se présenter sous forme de sel analogue au polymère ou autrement sous forme protégée, u = 0 ou 1, v = 1 à 60 et w = 1 à 20, et au moins l'un des radicaux R2, R3, R4, R5, R5, R6, R7 et R8 contient un radical aromatique ou araliphatique. L'invention concerne par ailleurs des agents mouillants et dispersants qui contiennent les polyéthers mentionnés ci-dessus ou se composent de ceux-ci, et un procédé pour préparer ces agents mouillants et dispersants, l'utilisation des polyéthers et des produits réactionnels du procédés selon l'invention en tant qu'agents mouillants et dispersants et des compositions contenant les polyéthers, des agents mouillants et/ou dispersants ou des produits réactionnels du procédé selon l'invention ainsi que des matières solides particulaires.
PCT/EP2017/079159 2016-11-15 2017-11-14 Polyéther à base d'oxétanes pour utilisation en tant qu'agents mouillants et dispersants, et leur utilisation Ceased WO2018091448A1 (fr)

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US3499759A (en) 1967-07-06 1970-03-10 Kalle Ag Light-sensitive reproduction layer comprising an oxetane polymer
EP0270126A2 (fr) 1986-12-05 1988-06-08 Byk-Chemie GmbH Composés d'addition utilisables comme dispersant ou stabilisateur de dispersion, leur procédé de préparation, leur utilisation et les solidesrevêtus avec ces composés
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JP2005068292A (ja) 2003-08-25 2005-03-17 Asahi Glass Co Ltd ポリエーテルモノオールまたはポリエーテルポリオールおよびその製造方法
US20060041032A1 (en) 2004-08-23 2006-02-23 Crivello James V Photopolymerizable epoxide and oxetane compositions
US20070144400A1 (en) 2003-12-22 2007-06-28 Mitsui Chemicales, Inc. Cationic polymerizable resin composition
US20110257326A1 (en) 2008-11-24 2011-10-20 Byk-Chemie Gmbh Compositions comprising glycidyl ether copolymers
EP2468835A1 (fr) 2009-08-21 2012-06-27 DIC Corporation Adhésif polymérisable par voie cationique et plaque de polarisation obtenue à l'aide de celui-ci
US8258189B2 (en) 2007-10-15 2012-09-04 Cecalc Compounds prepared by adding an oxetane derivative to an alcohol
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3499759A (en) 1967-07-06 1970-03-10 Kalle Ag Light-sensitive reproduction layer comprising an oxetane polymer
EP0270126A2 (fr) 1986-12-05 1988-06-08 Byk-Chemie GmbH Composés d'addition utilisables comme dispersant ou stabilisateur de dispersion, leur procédé de préparation, leur utilisation et les solidesrevêtus avec ces composés
DE3643007A1 (de) 1986-12-17 1988-06-30 Basf Ag Haertbare polyesterformmassen
US5130463A (en) 1989-09-14 1992-07-14 Byk-Chemie, Gmbh Phosphoric acid esters, method of producing them, and use thereof as dispersants
US6124402A (en) 1998-03-27 2000-09-26 Kanagawa University Polyaddition copolymer and process for producing the same
WO2002040572A1 (fr) 2000-11-14 2002-05-23 Perstorp Specialty Chemicals Ab Procede de fabrication d'un polyether dendritique
JP2005068292A (ja) 2003-08-25 2005-03-17 Asahi Glass Co Ltd ポリエーテルモノオールまたはポリエーテルポリオールおよびその製造方法
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US20110257326A1 (en) 2008-11-24 2011-10-20 Byk-Chemie Gmbh Compositions comprising glycidyl ether copolymers
EP2468835A1 (fr) 2009-08-21 2012-06-27 DIC Corporation Adhésif polymérisable par voie cationique et plaque de polarisation obtenue à l'aide de celui-ci
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