Patent Application
20240182746
The presently claimed invention relates to a polymer composition comprising at least one polyacrylic block copolymer and at least one aromatic based polyalkyleneoxide. The presently claimed invention is directed to a liquid composition in the form of a dispersion comprising the polymer composition. The presently claimed invention is also directed to a coating composition comprising the polymer composition as a dispersant.
Dispersions containing fine particulate solid materials such as pigments are widely used, e.g. as coating compositions, as printing inks, for preparing paint systems such as automotive, industrial and decorative paints, for coloring materials such as plastics and glasses and for manufacturing cosmetic compositions. An ideal dispersion consists of a homogenous and stable suspension of solid materials after size reduction or milling of any aggregates and agglomerates.
A dispersant improves various dispersion properties such as millbase viscosity and rheology behavior. The dispersant is also a determining factor of the aesthetics and physical properties of a coating. A dispersant can act as a flow control agent and bring about improved spreading of the coating composition over the surface of the substrate and improve the flow of the polymer film which forms in the course of curing, resulting in a smooth surface. As a consequence, the dispersant reduces the formation of defects, known as craters, which are caused by impurities acting from the outside or by impurities on the surface of the substrate.
It is well-known that pigments such as carbon black tend to re-aggregate over a period of time, thus leading to an inhomogeneity in the coating composition, and loss in gloss or jetness properties and a detrimental increase in viscosity in the compositions.
Due to increase environmental concerns, there is a growing need for coating compositions that can be formulated using water or predominantly water as solvent and dispersants play a very important role in providing stable, water-based coating compositions.
In view of the wide application of dispersions containing fine particulate solid materials and the important role played by the dispersants in their preparation, stability and properties, there is a growing need for improved dispersants that are capable of assisting the preparation of dispersions having the desired characteristics.
The controlled free radical polymerisation (CFRP) is a tool to tailor the microstructure of polymers (e.g. block copolymers) in a way that is favourable for dispersing and stabilizing pigments. With the CFRP-process a large row of different polymer materials for either waterborne or also solvent-borne high solids systems have become available.
However, the use of polymers obtained by CFPR process are associated with some limitations such as high viscosity of millbase, which limits the amount of pigment concentration in millbase, crater issue in some let down systems. The usefulness of the polymer obtained by CFRP as a dispersant can be further improved to modify overall functioning and solubility in water based coatings.
Accordingly, it is an object of the presently claimed invention to provide a dispersant having improved properties such as a low millbase viscosity, and which provides a coating composition having improved coating properties without adversely affecting its color properties.
It was surprisingly found that a polymer composition comprising at least one polyacrylic block copolymer and at least one aromatic based polyalkyleneoxide provides a dispersant having improved dispersion properties such as a low millbase viscosity. The coating compositions comprising the polymer composition of the presently claimed invention provides surface coats having favourable properties such as a low crater ranking. Further, the dispersant composition does not adversely affect the color properties of the coating composition.
Accordingly, one aspect of the presently claimed invention is a polymer composition comprising
R1R2NOX (I), and
R1R2NO· (II);
T-(O—P)n—NH2 (III)
Another aspect of the presently claimed invention is directed to a method for preparing the polymer composition of the present invention comprising the steps of
Another aspect of the presently claimed invention is directed to a liquid composition in the form of a dispersion comprising
Another aspect of the presently claimed invention is directed to a coating composition comprising the dispersant composition of the presently claimed invention.
Another aspect of the presently claimed invention is directed to use of the polymer composition of the presently claimed invention as a dispersant in a coating composition.
Before the present compositions and formulations of the presently claimed invention are described, it is to be understood that this invention is not limited to particular compositions and formulations described, since such compositions and formulation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the presently claimed invention will be limited only by the appended claims.
If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms ‘first’, ‘second’, ‘third’ or ‘a’, ‘b’, ‘c’, etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the presently claimed invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms ‘first’, ‘second’, ‘third’ or ‘(A)’, ‘(B)’ and ‘(C)’ or ‘(a)’, ‘(b)’, ‘(c)’, ‘(d)’, ‘i’, ‘ii’ etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
Furthermore, the ranges defined throughout the specification include the end values as well i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, applicant shall be entitled to any equivalents according to applicable law.
In the following passages, different aspects of the presently claimed invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Reference throughout this specification to ‘one embodiment’ or ‘an embodiment’ means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the presently claimed invention. Thus, appearances of the phrases ‘in one embodiment’ or ‘in an embodiment’ in various places throughout this specification are not necessarily all referring to the same embodiment but may refer to so.
Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the presently claimed invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.
Accordingly, the one aspect of the presently claimed invention is a polymer composition comprising
R1R2NOX (I), and
R1R2NO· (II);
T-(O—P)n—NH2 (III)
Within the context of the presently claimed invention, the term alkyl, as used herein, refers to an acylic saturated aliphatic groups, including linear alkyl saturated hydrocarbon radical denoted by a general formula CnH2n+1 and wherein n is the number of carbon atoms 1, 2, 3, 4 etc.
Examples of linear unsubstituted C1 to C22 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl and docosyl.
Examples of branched unsubstituted C1 to C22 alkyl are 1-methyl ethyl, 1-methyl propyl, 2-methyl propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-methyl pentyl, 2-methyl pentyl, 3-methyl pentyl, 4-methyl pentyl, 1-methyl hexyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, 1-methyl heptyl, 2-methyl heptyl, 3-methyl heptyl, 4-methyl heptyl, 5-methyl heptyl, 6-methyl heptyl, 1-methyl octyl, 2-methyl octyl, 3-methyl octyl, 4-methyl octyl, 5-methyl octyl, 6-methyl octyl, 7-methyl octyl, 1-methyl nonyl, 2-methyl nonyl, 3-methyl nonyl, 4-methyl nonyl, 5-methyl nonyl, 6-methyl nonyl, 7-methyl nonyl, 8-methyl nonyl, 1-methyl decyl, 2-methyl decyl, 3-methyl decyl, 4-methyl decyl, 5-methyl decyl, 6-methyl decyl, 7-methyl decyl, 8-methyl decyl, 9-methyl decyl, 1-methyl undecyl, 2-methyl undecyl, 3-methyl undecyl, 4-methyl undecyl, 5-methyl undecyl, 6-methyl undecyl, 7-methyl undecyl, 8-methyl undecyl, 9-methyl undecyl, 10-methyl undecyl, 1-ethyl propyl, 1-ethyl butyl, 2-ethyl butyl, 1-ethyl pentyl, 2-ethyl pentyl, 3-ethyl pentyl, 1-ethyl hexyl, 2-ethyl hexyl, 3-ethyl hexyl, 4-ethyl hexyl, 1-ethyl heptyl, 2-ethyl heptyl, 3-ethyl heptyl, 4-ethyl heptyl, 5-ethyl heptyl, 1-ethyl octyl, 2-ethyl octyl, 3-ethyl octyl, 4-ethyl octyl, 5-ethyl octyl, 6-ethyl octyl, 1-propyl butyl, 1-propyl pentyl, 2-propyl pentyl, 1-octyl nonyl, 1-octyl decyl, 2-octyl decyl, 1-octyl undecyl, 2-octyl undecyl, 3-octyl undecyl, 1-octyl dodecyl, 2-octyl dodecyl, 3-octyl dodecyl and 4-octyl dodecyl.
Within the context of the presently claimed invention, the term hydroxy-C1-C6-alkyl refers to alkyl having 1 to 6 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a hydroxy group. Examples of hydroxy-C1-C6 alkyl are 1-hydroxy ethyl, 1-hydroxy propyl, 2-hydroxy propyl, 1-hydroxy butyl, 2-hydroxy butyl, 3-hydroxy butyl, 1-hydroxy pentyl, 2-hydroxy pentyl, 3-hydroxy pentyl, 4-hydroxy pentyl, 1-hydroxy hexyl, 2-hydroxy hexyl, 3-hydroxy hexyl, 4-hydroxy hexyl and 5-hydroxy hexyl.
Within the context of the presently claimed invention, the term cycloalkyl, as used herein, refers to a monocyclic and a bicyclic 3 to 10 membered saturated cycloaliphatic groups, including branched cycloalkyl saturated hydrocarbon. Preferably, the cycloalkyl refers to C1 to C6 carbon atoms, selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Within the context of the presently claimed invention, the term alkylene refers to an acyclic saturated hydrocarbon chains, which combine different moieties. Preferably, the alkylene refers to linear unsubstituted C1 to C4 carbon atoms, selected from the group consisting of —CH2—, —CH2—CH2—, —CH2—CH2—CH2— and —CH2—CH2—CH2—CH2—.
Within the context of the presently claimed invention, the term arylalkyl, as used herein, refers to alkyl having 5 to 24 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a aryl radical.
Within the context of the presently claimed invention, the term heteroaryl, as used herein, refers to C5-C10 heteroaromatic groups, for example pyrrole, pyrazole, imidazole, 2,4, dimethylpyrrole, 1-methylpyrrole, thiophene, furan, furfural, indole, cumarone, oxazole, thiazole, isoxazole, isothiazole, triazole, pyridine, α-picoline, pyridazine, pyrazine or pyrimidine.
Within the context of the presently claimed invention, the term alkinyl, as used herein, refers to a linear unsaturated aliphatic groups with 3 to 18 carbon atoms such as propinyl (—CH2—C═CH), 2-butinyl, 3-butinyl, n-2-octinyl, or n-2-octadecinyl.
Examples for halogen substituted alkyl are dichloropropyl, monobromobutyl or trichlorohexyl. C2-C18 alkyl interrupted by at least one O atom is for example —CH2—CH2—O—CH2—CH3, —CH2—CH2—O—CH3— or —CH2—CH2—O—CH2—CH2—CH2—O—CH2—CH3—. It is preferably derived from polyethlene glycol. A general description is —((CH2)a—O)b—H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
In a more preferred embodiment, the polymer composition comprises
R1R2NOX (I),
T-(O—P)n—NH2 (III)
In a more preferred embodiment, the polymer composition comprises
In an even more preferred embodiment, the polymer composition comprises
In a most preferred embodiment, the polymer composition comprises
The first polymerization step is controlled free radical polymerization (CFRP) of at least one acrylate monomer selected from C1-C6 alkyl esters of acrylic acid, C1-C6 alkyl esters of methacrylic acid, hydroxy C1-C6 alkyl esters of acrylic acid and hydroxy C1-C6 alkyl esters of methacrylic acid.
In a more preferred embodiment, the at least one acrylate monomer is selected from C1-C6 alkyl esters of acrylic acid.
In a most preferred embodiment, the at least one acrylate monomer is selected from n-butyl acrylate and 2-ethyl hexyl arylate.
In the second polymerization step, the polymer obtained in the first polymerization step is reacted with at least one ethylenically unsaturated monomer selected from a C5-C20 vinylaromatic, an ethylenically unsaturated nitrile, acrylamide, a vinyl halide, a vinyl ether of an C1-C10 alcohol and an C2-C8 aliphatic hydrocarbon having one or two double bonds.
In a preferred embodiment, the at least one ethylenically unsaturated monomer are selected from isoprene, 1,3-butadiene, α—C5-C18 alkene, 4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole or imidazolinium-ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methyl styrene, p-tert-butyl-styrene and
CH2═C(Ra)—(C═Z)—Rb,
In a more preferred embodiment, Ra is hydrogen or methyl, Rb is selected from NH2, glycidyl, unsubstituted or with hydroxy substituted C1-C4 alkoxy, unsubstituted C1-C4 alkylamino, di(C1-C4 alkyl)amino, hydroxy-substituted C1-C4 alkylamino and hydroxy-substituted di(C1-C4 alkyl)amino; and Z is oxygen.
Examples for Rb as C2-C100 alkoxy interrupted by at least one O atom are of formula,
These monomers are for example derived from non-ionic surfactants by acrylation of the corresponding alkoxylated alcohols or phenols. The repeating units may be derived from ethylene oxide, propylene oxide or mixtures of both.
Further examples of suitable acrylate or methacrylate monomers are given below.
Further acrylate monomers are
In an even more preferred embodiment, the at least one ethylenically unsaturated monomer is selected from 3-dimethylaminopropylmethacrylamide, 2-vinyl-pyridine, 4-vinyl-pyridine, dimethylaminoethyl methacrylate, hydroxyethylacrylate, hydroxyproylacrylate, n-butylacrylate, and styrene.
In a most preferred embodiment, the at least one ethylenically unsaturated monomer is selected from 2-vinyl-pyridine, 4-vinyl-pyridine, 3-diemthylaminopropylmathylacrylamide and dimethylaminoethyl methacrylate.
Examples for suitable ethylenically unsaturated monomer other than acrylates are
In a preferred embodiment, the ethylenically unsaturated monomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic acid-anhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (alkyl)acrylonitriles, (alkyl)acryl-amides, vinyl halides and vinylidene halides.
In a preferred embodiment, the ethylenically unsaturated monomer is selected from styrene, substituted styrene, methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert-butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, methyl(meth)acrylate, ethyl-(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, meth-acrylamide and dimethylaminopropyl-methacrylamide.
It is also possible to use mixtures of the aforementioned monomers, in particular styrene/acrylonitrile, styrene/butylacrylate, styrene/methylmethacrylate and styrene/butyl methacrylate.
All possible polymer chain structures are comprised: e.g. linear or branched. If the monomers are selected from chemically different monomers, all possible monomer sequence structures are comprised, e.g. random-, blocklike, multiblock-, tapered- or gradient arrangement of the different monomers.
In a preferred embodiment, the above described controlled free radical polymerization process is carried out twice to obtain a block copolymer.
In a preferred embodiment, the block copolymer is a gradient block copolymer.
Under gradient polymers or gradient arrangement there are understood block copolymers, which are prepared in such a way, that the intersection between the two blocks is not a sharp boundary, but represents a continuous transition from one type of monomer to another type of monomer, i.e. both monomers extending to both blocks. This type of polymers can be obtained when the polymerization process is carried out for example in one step using monomers of different copolymerization parameters or by a multistep procedure, in which the monomer composition is stepwise changed by addition of appropriate amounts of another type of monomer. Another preferred procedure for the synthesis of gradient polymers is by using continuous feed processes, in which for example the controlled polymerization is started with a first monomer and before complete conversion, a second monomer is continuously fed to the reaction mixture, thus realizing a continuous transition along the polymer chains. When controlled free radical polymerization is carried out twice and a block copolymer is obtained for example the monomer or monomer mixture of the first radical polymerization contains from 50 to 100% by weight based on total monomers of a C1-C4 alkyl or hydroxyalkyl ester of acrylic or methacrylic acid and the second radical polymerization contains a monomer or monomer mixture possessing the ethylenically unsaturated monomer.
In a preferred embodiment, the controlled free radical polymerization is carried out in the presence of a1.
In a preferred embodiment, the controlled free radical polymerization is carried out in the presence of a2.
Suitable nitroxylethers and nitroxyl radicals are principally known from U.S. Pat. No. 4,581,429 or EP-A-621 878.
Particularly useful are the open chain compounds described in WO 98/13392 (Akzo), WO 99/03894 (Ciba) and WO 00/07981 (Ciba), the piperidine derivatives described in WO 99/67298 (Ciba) and GB 2335190 (Ciba) or the heterocyclic compounds described in GB 2342649 (Ciba)and WO 96/24620 (Atochem).
Further suitable nitroxylethers and nitroxyl radicals are described in WO 02/4805 (Ciba) and in WO 02/100831 (Ciba).
Nitroxylethers and nitroxyl radicals with more than one nitroxyl group in the molecule are for example described in U.S. Pat. No. 6,573,347 (Ciba), WO 01/02345 (Ciba) and WO 03/004471 (Ciba).
In the context of the present invention the terms alkoxyamine and nitroxylether are used as equivalents.
Stable free radicals having a structural element N—O* are for example disclosed in EP-A-621 878 (Xerox).
Examples of such as are given in WO96/24620
In a preferred embodiment, the structural element N—O—X or N—O* is part of a 5 or 6-membered heterocyclic ring, which optionally has an additional nitrogen or oxygen atom in the ring system.
In a more preferred embodiment, the structural element N—O—X or N—O* is part of a substituted piperidine, morpholine and piperazine derivatives.
In a preferred embodiment, the structural element N—O—X is a structural element of formula (Ia)
CH3CH—CH═CH2, (C1-C4 alkyl)CR20—C(O)-phenyl, (C1-C4)alkyl-CR20—C(O)—(C1-C4)alkoxy, (C1-C4)alkyl-CR20—C(O)—(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—N-di(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—NH(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—NH2, wherein R20 is hydrogen or (C1-C4)alkyl and * denotes a valence.
In a preferred embodiment, the structural element N—O* is a structural element of formula (IIa)
In a preferred embodiment, the structural element N—O—X is of formula A, B or O,
—CH2CH═CH2, CH3CH—CH═CH2, (C1-C4 alkyl)CR20—C(O)-phenyl, (C1-C4)alkyl-CR20—C(O)—(C1-C4)alkoxy, (C1-C4)alkyl-CR20—C(O)—(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—N-di(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—NH(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—NH2, wherein R20 is hydrogen or (C1-C4)alkyl.
In a preferred embodiment, the structural element N—O* is of formula A′, B′ or O′,
The above compounds and their preparation are described in GB2335190 and GB2361235.
In a preferred embodiment, the structural element N—O—X are of formula (Ic), (Id), (Ie), (If), (Ig) or (Ih)
—CH2CH═CH2, CH3CH—CH═CH2, (C1-C4 alkyl)CR20—C(O)-phenyl, (C1-C4)alkyl-CR20—C(O)—(C1-C4)alkoxy, (C1-C4)alkyl-CR20—C(O)—(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—N-di(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—NH(C1-C4)alkyl, (C1-C4)alkyl-CR20—C(O)—NH2, wherein R20 is hydrogen or (C1-C4)alkyl.
More preferably in formula (Ic), (Id), (Ie), (If), (Ig) and (Ih) at least two of R201, R202, R203 and R204 are ethyl, propyl or butyl and the remaining are methyl; or
Most preferably X is CH(CH3)-phenyl.
The above compounds and their preparation are described in GB 2342649.
In a preferred embodiment, the structural elements N—O—X and N—O* are 4-imino compounds of formula (III) or (IV)
Preferably G16 is hydrogen and G16 is hydrogen or C1-C4 alkyl, in particular methyl, and G11 and G13 are methyl and G12 and G14 are ethyl or propyl or G11 and G12 are methyl and G13 and G14 are ethyl or propyl.
The 4 imino compounds of formula (III) or (IV) can be prepared for example according to E. G. Rozantsev, A. V. Chudinov, V. D. Sholle.: Izv. Akad. Nauk. SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group. The compounds are described WO 02/100831 (Ciba).
In a preferred embodiment, the controlled free radical polymerization process is carried out in the presence of a1). The nitroxylether of formula (I) according to the structures outlined above splits between the O—X bond. The regulating fragment in formula (I) corresponds to the O—N fragment and the initiating fragment (In) corresponds to the C centred radical of the group X.
In a more preferred embodiment, suitable nitroxylethers and nitroxyl radicals are those of formulae:
In a particularly preferred embodiment, the at least one nitroxylether is a compound of formula (Ia).
In a preferred embodiment, the initiator compound (a1 or a2) is present in an amount of from 0.01 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.1 mol-% to 10 mol-% based on the amount of the monomer or monomer mixture.
When monomer mixtures are used, mol % is calculated on the average molecular weight of the mixture.
When the controlled free radical polymerization is carried out in the presence of a2, the free radical initiator is preferably an azo compound, a peroxide, perester or a hydroperoxide.
In a more preferred embodiment, the free radical initiator are 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methyl-butyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane), 2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base or hydrochloride, 2,2′-azobis(2-amidinopropane), free base or hydrochloride, 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxy-methypethyl]propionamide} or 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxy-ethyl]propionamide; acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy) butane, 2,2 bis(t-butylperoxy)propane, dicumyl peroxide, 2,5-dimethyl hexane-2,5-di-t-butylperoxide, 3-t-butyl peroxy 3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl-1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.
In a preferred embodiment, the free radical initiator is present in an amount of from 0.01 mol-% to mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-% and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the amount of the monomer or monomer mixture.
In a preferred embodiment, the molar ratio of the free radical initiator to the nitroxyl radical is in the range from 1:10 to 10:1, more preferably from 1:5 to 5:1, and most preferably from 1:2 to 2:1.
In a preferred embodiment, the polymer or copolymer prepared according by the controlled free radical polymerization has a molecular weight (Mw) in the range from 2,000 g/mol to 50,000 g/mol, more preferably from 5,000 g/mol to 30,000 g/mol, and most preferably from 8,000 g/mol to 20,000 g/mol.
In a preferred embodiment, the polymer or copolymer prepared according by the controlled free radical polymerization has a polydispersity index of 1.0 to 2.2, more preferably from 1.1 to 1.9, and most preferably from 1.1 to 1.5.
The polyacrylic block copolymer is optionally subjected to functionalization by transesterification with at least one alcohol. In transesterification, the alcohol radical in an ester group of the polymer or copolymer is replaced by another alcohol radical.
In a preferred embodiment, the at least one polyacrylic block copolymer is subjected to functionalization with at least one alcohol selected from W1 and W2,
G-(O-Q)n-OH
Typically, the transesterification reaction is carried out at elevated temperatures, typically 70-200° C., by reacting the polymer obtained from CFRP with the corresponding alcohol in the presence of well-known catalysts, such as tetra-isopropyltitanate, tetra-butyltitanate, alkali- or earth alkali alcoholates like NaOMe or LiOMe. Typically, the low boiling product alcohol is removed from the transterification reaction mixture by distillation. If required, catalyst residues may be removed by adsorption or extraction or otherwise processed or inactivated by known methods, like hydrolysis with water or acids.
The choice of the replacing alcohol is important as the replacing alcohol controls the properties of the resulting copolymer.
By using a polar replacing alcohol such as alcohols having e.g. the following formula R—[O—CH2—CH2—]n—OH, e.g. methoxypolyethylene glycol (MPEG-OH), a water-soluble resulting polymer can be obtained. The solubility depends on the amount of transesterified monomer units. At least 40% of the units should be transesterified to obtain the desired effect.
If the solubility in organic solvents is required, nonpolar alcohols like higher molecular weight branched aliphatic alcohols can be beneficial.
If polymers with low surface tension are desired, alcohols containing siloxane groups are preferred, e.g. with the following formula
or partly or fully fluorinated primary alcohols can be used instead or in addition.
If a solid copolymer is required, solid alcohols or polar alcohols which are able to raise the glass transition temperature (Tg) or impart side chain crystallinity should be used. An example is behenyl alcohol.
The replacing alcohol radical is typically an aliphatic C6-C36 alcohol or a precursor of an alcohol, having at least one —OH group. The alcohol may also be interrupted by 1 to 20 O or N atoms or substituted by halogen, perfluoralkyl, NH2, NH(C1-C18 alkyl), N(C1-C18 alkyl)2, COO(C1-C18 alkyl), CON(C1-C18 alkyl)2, CONH(C1-C18 alkyl), CONH2, COOH, COO−, O(C1-C18 alkyl) or with a Si, P or S containing group, for example alkylhydroxysilicones. The alcohol may also contain heterocyclic ring structures, such as 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-(2-hydroxyethyl)pyridine, N-2-hydroxyethyl)phtalimide, 4-(2-hydroxyethyl)morpholine, 1-(2-hydroxyethyl)piperazine, N-hydroxymethylphthalimide, 3-hydroxymethylpyridine or (4-pyridyl)-1-propanol.
The alcohols, which are interrupted by O or N atoms are not limited to 36 C atoms. These can be oligomeric or polymeric alcohols also. Examples of alcohols interrupted by O atoms are methoxypolyethyleneglycols or adducts of ethyleneoxide and/or propylene-oxide (EO/PO). Such EO/PO-adducts can be random or block type structures.
In a more preferred embodiment, the alcohol is an unsubstituted linear or branched C8-C36 alkyl monoalcohol or a monoalcohol derived from ethylenoxide, propylenoxide or mixtures thereof with up to 100 C atoms.
In an even more preferred embodiment, the alcohol is methoxypolyethyleneglycol (MPEG-OH).
In an embodiment, the at least one polyether alcohol is methoxypolyethyleneglycol with the molecular weight (Mw) of 200-1000 g/mol.
It is also possible to use fatty acid alcohol ethoxylates, alkylphenolethoxylates, alkoxylates of all kinds of monofunctional alcohols or phenols or secondary amines. Preferably the alkoxylate is an ethoxylate of a primary alcohol or alkylphenol of structure (A):
R—[O—CH2—CH2—]n—OH (A)
wherein R is saturated or unsaturated, linear or branched chain alkyl with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is 1 to 50.
Referring to another embodiment the alcohol is an unsubstituted linear or branched C8-C36 alkyl mono alcohol or mixtures thereof. An example is a mixture of iso C12-C15 alcohol. Non-polar polymers or copolymers are obtained.
In another embodiment, the macroalcohol is a primary OH-functional silicone oligomer. Preferred are polydimethylsilicone oligomers of structure (B):
In another embodiment the alcohol is a partly or fully fluorinated primary alcohols. Examples of commercial fluorinated alcohol mixtures are: Zonyl BA®, Zonyl BA-L®, Zonyl BA-LD®, Zonyl BA-N® from Du Pont.
Precursors of alcohols are for example macroalcohols, such as poly-ε-caprolactone oligomers or ε-caprolactone adducts and similar lactone adducts (e.g. based on valerolactone) or mixed adducts of ε-caprolactone and valerolactone. Typical lactone adducts are adducts of ε-caprolactone to long chain fatty alcohols of structure:
R—[O—CO—CH2—CH2—CH2—CH2—CH2—]n—OH
wherein R is saturated or unsaturated, linear or branched chain alkyl with 8-22 carbon atoms or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is 1 to 50. It is also possible to use macroalcohols based on polyolefins, which have typically molecular weights (Mw) up to 5000, preferably up to 2000.
Yet another embodiment are unsaturated alcohols containing carbon-carbon double bonds or carbon triple bonds. An example is oleyl alcohol. Regarding triple bond preferred are primary alkinols like propargyl alcohol and higher homologues like alkylsubstituted propargylalcohol.
Preferably the alcohol is a monoalcohol and is a primary or secondary alcohol. Most preferred are primary alcohols or alcohol mixtures like Lial 125.
Preferably the alcohol or alcohol mixture is non-volatile and has a boiling point or range of at least 100° C., more preferably of at least 200° C.
The aromatic based polyalkyleneoxide bear at least one, e.g. on an average 1 to 250, in particular 2 to 150 and especially 5 to 100 aromatic moieties P.1 per polymer molecule. In this context, the term “on average” is understood as the number average. Each of the moieties P.1 is bound to a nitrogen atom of the polyalkylene imine backbone via a carboxamide or carboximide group.
The aromatic moiety P.1 comprises either an optionally substituted aryl, which is bound to a nitrogen atom of the polyethylene imine radical via a carbonyl group, thereby forming a carboxamide group, or an optionally substituted arylene radical which is bound to a nitrogen atom of the polyethylene imine radical via two carbonyl groups, thereby forming a carboximide group. The aryl or arylene moieties of P.1 are unsubstituted or substituted, e.g. by 1, 2, 3, 4 or 5 radicals, which are preferably selected from halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, COOH, CONH2, NH2, NO2, NH—CHO, NH—C1-C4-alkyl, and NH—(C═O)—C1-C4-alkyl.
Within the aromatic based polyalkyleneoxide, the radicals P.1 may be identical or different. Preferably, they are identical.
The moieties P.1 will generally contribute by an amount of 1 to 25% by weight, in particular from 1.5 to 15% by weight or from 2 to 10% by weight to the total weight of the polymer. The relative amount of the moieties P.1 to the polyalkylene imine may be from 10 to 200% by weight, in particular from 20 to 150% by weight.
In a preferred embodiment, the moiety P.1 is selected from the moieties of the formula (P.1′) and (P.1″)
In this context, Ar and Ar′ preferably have the following meanings:
In the context of formulae P.1′, P.1″, the substituents Ron phenylene or naphthylene, if present, are in particular selected from the group consisting of Cl, NH2, NO2, COOH, NH—CHO, NH—CH3, and NH—(C═O)—CH3.
In particular, the moiety P.1 is selected from the group consisting of radicals of the formulae (P.1a), (P.1b), (P.1c), (P.1d), and (P.1e),
In the context of formulae P.1a, P.1b, P.1c, P.1d and P.1e, the radical R, if present, is in particular selected from the group consisting of Cl, NH2, NO2, NH—CHO, NH—CH3, and NH—(C═O)—CH3.
Examples of moieties P.1 include 2-aminophenylcarbonyl (P.1a with q=0), 2,5-diaminophenylcarbonyl (P.1a with q=1, R=5-NH2), 2-amino-5-bromophenylcarbonyl (P.1a with q=1, R=5-Br), 2-carboxyphenylcarbonyl (P.1 b with q=0), 2,4-dicarboxyphenylcarbonyl (P.1b with q=1, R=4-COOH), 8-carboxynaphthyl-1-carbonyl (P.1c with q=0), 3-bromo-8-carboxynaphthyl-1 -carbonyl (P.1c with q=1, R=3-bromo), 6-bromo-8-carboxynaphthyl-1-carbonyl (P.1c with q=1, R=6-bromo), 3-nitro-8-carboxynaphthyl-1-carbonyl (P.1c with q=1, R=3-NO2), 4-nitro-8-carboxynaphthyl-1-carbonyl (P.1c with q=1, R=4-NO2), 5-nitro-8-carboxynaphthyl-1-carbonyl (P.1c with q=1, R=5-NO2), 6-nitro-8-carboxynaphthyl-1-carbonyl (P.1c with q=1, R=6-NO2), 1,2-phenylendicarbonyl (radical P.1d with q=0), 4-carboxy-1,2-phenylendicarbonyl (radical P.1d with q=1, R=4-COOH), 1,8-nahpthylendicarbonyl (radical P.1e with q=0), 3-bromo-1,8-nahpthylendicarbonyl (radical P.1e with q=1, R=3-Br), 3-nitro-1,8-nahpthylendicarbonyl (radical P.1e with q=1, R=3-NO2), 4-nitro-1,8-nahpthylendicarbonyl (radical P.1e with q=1, R=4-NO2).
The polymers of the invention bear at least one, e.g. on average 1 to 400, in particular 5 to 250 and especially 10 to 150 aliphatic polyester moieties P.2 per polymer molecule. In this context, the term “on average” is understood as the number average. Each of the moieties P.2 is bound to a nitrogen atom of the polyalkylene imine backbone via a carboxamide group. The term “aliphatic” means that the polyester groups do not contain aromatic rings. In particular, the polyester radicals bear repeating units having a C2-C8-alkylene moiety, which is unsubstituted or carries 1, 2, 3, or C1-C4-alkyl radicals. Within the polymers of the invention, the moieties P.2 may be identical or different. Preferably, they are identical.
The moieties P.2 will generally contribute by an amount of 50 to 98% by weight, in particular from 70 to 97% by weight or from 80 to 96% by weight to the total weight of the polymer. The weight ratio of the moieties P.2 to the polyalkylene imine is generally in the range from 1:1 to 98:1, in particular from 2:1 to 97:1 or from 3:1 to 50:1.
Preferably, the moiety P.2 is
The variables A and Rx in the at least one moiety (P.2) have in particular the following meanings:
The polymers of the invention have a polyalkylenimine backbone, to which the at least one moiety P.1 and the at least one moiety P.2 are attached.
The polyalkylene imine may be linear or branched. The polyalkylene imine is in particular a linear or branched poly(C2-C4-alkyleneimine), more particularly a linear or branched polypropylene imine, a linear or branched poly(ethylene imine-co-propylene imine) or a linear or branched polyethylene imine or a mixture thereof. Especially, the polyalkylene imine, which forms the backbone, is a linear or branched polyethylene imine.
The polyalkylene imine will usually have on average from 5 to 500, in particular from 10 to 250 especially from 20 to 100 alkylene imine repeating units, which corresponds to a number average molecular weight of the polyalkylene imine backbone in the range from about 200 to 20000 g/mol, in particular in the range from 400 to 10000 g/mol and especially in the range from 800 to 5000 g/mol.
The polyalkylene imine backbone will generally contribute by an amount of 1 to 25% by weight, in particular from 1.5 to 15% by weight or from 2 to 10% by weight to the total weight of the polymer.
Both moieties P.1 and P.2 are attached to nitrogen atoms of the polyalkylene imine backbone. As these nitrogen atoms are part of a carboxamide or carboximide group, their basicity is low compared to nitrogen atoms of a non-modified polyalkylene imine. It is apparent to a skilled person that polymers of the invention may have nitrogen atoms, which do not carry moieties P.1 and P.2. These nitrogen atoms are basic and susceptible to protonation or quaternization. Polymers of the invention, which have nitrogen atoms, which do not carry moieties P.1 and P.2, will usually have an amine number >0 mg KOH/g, e.g. in the range from 2 to 150 mg KOH/g, in particular from 5 to 50 mg KOH/g.
As explained above, polymers of the invention, which have an amine number >0 mg KOH/g, e.g. in the range from 2 to 150 mg KOH/g, in particular from 5 to 50 mg KOH/g are susceptible to protonation or quaternization, which means that at least some of the nitrogen atoms of the polyalkylene imine backbone that do not carry moieties P.1 or P.2, hence amino groups of the polyalkylene imine backbone, can be transformed into cationic, i.e. into protonated or quaternized amino groups. Therefore, one embodiment of the invention relates to polymers, wherein the polyalkylene imine backbone in addition to the moieties P.1 and P.2 has protonated or quaternized amino groups. In this embodiment, the amount of protonated or quaternized amino groups is generally from 0.01 to 0.5 mol/kg.
Another embodiment of the invention relates to polymers, wherein the polyalkylene imine backbone in addition to the moieties P.1 and P.2 does not have quaternized amino groups. In this embodiment, the amount of quaternized amino groups is less than 0.01 mol/kg.
Depending of the type of amino nitrogen atom (primary, secondary, or tertiary), the protonated or quaternized amino groups can be described by the following formulae Q1, Q2 and Q3:
where Rk indicates a H (protonized groups Q1, Q2 and Q3) or an optionally substituted hydrocarbon radical such as alkyl, aryl, arylalkyl or cycloalkyl (quaternized groups Q1, Q2 and Q3).
Preferably, Rk is selected from the group consisting of
In particular Rk is selected from the group consisting of
The positive charge of the quaternized or protonized groups is neutralized by suitable anions including halogenide, such as chloride or bromide, sulfate (SO42−), hydrogensulfate (HSO4−), alkylcarboxylate, such as acetate or propionate, arylcarboxylates, where the aryl ring is unsubstituted or optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, NO2, hydroxyl or halogen, such as benzoate, C1-C4-alkylbenzoate, 2-hydroxybenzoate, 4-hydroxybenzoate, 1-naphthoate, 2-naphthoate, 2-hydroxy-3-naphthoate, 8-hydroxy-1-naphthoate, C1-C4-alkyl-sulfonate, such as methylsulfonate or ethylsulfonate, C1-C4-alkylsulfate such as methyl sulfate or ethyl sulfate, arylsulfonates, where the aryl ring is unsubstituted or optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, NO2, hydroxyl or halogen, such as benzene sulfonate, toluene sulfonate or naphthalin sulfonate.
In a preferred embodiment, the at least one monoamine functionalized polyalkyleneoxide is methoxypolyethyleneglycolamine, methoxypolypropyleneglycolamine, methoxypoly(ethylene-co-propylene)glycolamine.
In a preferred embodiment, the at least one aromatic compound is selected from isatoic anhydride and naphthalic anhydride.
Another aspect of the presently claimed invention is directed to a method for preparing the polymer composition of the present invention comprising the steps of
In an embodiment, the step (ii) of mixing is carried out at a temperature in the range from 30° C. to 120° C. for a time period in the range from 0.5 h to 24 h.
Yet another aspect of the presently claimed invention is directed to a liquid composition in the form of a dispersion comprising
In a preferred embodiment, the liquid composition is a millbase.
In a preferred embodiment, the particulate solid material is a pigment.
In a preferred embodiment, the organic pigment (or a mixture of organic pigments), the polymer composition according to the presently claimed invention as a dispersant and a milling liquid such as water (or a mixture of miling liquids), and, optionally, one or more milling additives and/or one or more surface treatment additives are combined in any order. Preferably, all such components are combined prior to the milling such that the total solids content in the milling mixture is at least about 10% by weight (more preferably 20 to 50% by weight).
Milling is carried out using known dry milling methods, such as jet milling, ball milling, and the like, or known wet-milling methods, such as salt kneading, sand milling, bead milling, and the like.
Another aspect of the presently claimed invention is directed to a coating composition comprising the dispersant composition of the presently claimed invention.
In a preferred embodiment, the dispersant composition is a millbase.
It is observed that the liquid compositions comprising the polymer composition of the presently claimed invention have a low millbase viscosity.
In a preferred embodiment, the dispersant composition is a millbase comprising a black pigment.
In a preferred embodiment, the coating composition further comprises at least one additive selected from pigment pastes, binders, fillers, solvents, defoamers, neutralising agent, wetting agent, pigment dispersing agents, preservatives and water.
In a preferred embodiment, the coating composition is water based coating composition comprising waterborne acrylic copolymer dispersion.
Another aspect of the presently claimed invention is directed to use of the polymer composition of the presently claimed invention as a dispersant in a coating composition.
Pigments prepared according to the presently claimed invention are suitable for use in a variety of pigment applications, particularly in view of their excellent dispersibility without sacrificing color properties in wet and/or dried coating systems. Pigments produced from the processes of the present invention are highly dispersible without sacrificing color properties in wet and/or dried coating systems. For example, the conditioned pigments can be dried and used as components in coating systems. Conditioned pigments prepared by the processes of the present invention are readily dispersible, for example, in aqueous coating systems. The conditioned pigments may be mixed with other materials such as pigment formulations (including inorganic white pigments, such as titanium dioxide (rutile), cement, inorganic pigments, flushed pastes with organic liquids or pastes, pigment dispersions with water, dispersants, and, if appropriate, preservatives), coating compositions (including paints, preferably automotive paint, electronic coating paints, physically or oxidatively drying lacquers, stoving enamels, reactive paints, two-component paints, solvent- or water-based paints, emulsion paints for weatherproof coatings and distempers, printing ink, including ink jet inks, or colored paper).
The presently claimed invention offers one or more of the following advantages:
In the following, there are provided a list of embodiments to further illustrate the present disclosure without intending to limit the disclosure to specific embodiments listed below.
1. A polymer composition comprising
R1R2NOX (I), and
R1R2NOX· (II);
T-(O—P)n—NH2 (III)
2. The polymer composition according to embodiment 1, wherein the at least one acrylate monomer is n-butyl acrylate, or 2-ethyl hexyl arylate.
3. The polymer composition according to embodiment 1 or 2, wherein the at least one nitroxylether is a compound of formula (Ia).
4. The polymer composition according to any of embodiments 1 to 3, wherein the at least one ethylenically unsaturated monomer is selected from isoprene, 1,3-butadiene, α—C5-C18-alkene, 4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole or imidazolinium ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methyl styrene, p-tert-butyl-styrene and
CH2═C(Ra)—(C═Z)—Rb,
5. The polymer composition according to any of embodiments 1 to 4, wherein the at least one ethylenically unsaturated monomer is selected from 2-vinylpyridine, 4-vinyl-pyridine, 3-diemthylaminopropylmathylacrylamide and dimethlyaminoethyl methacrylate.
6. The polymer composition according to embodiments 1 to 5, wherein the at least one polyacrylic block copolymer is subjected to functionalization with at least one alcohol selected from W1 and W2,
7. The polymer composition according to embodiment 6, wherein the at least one polyether alcohol is methoxypolyethyleneglycol with the molecular weight (Mw) of 200-1000 g/mol.
8. The polymer composition according to any of embodiments 1 to 7, wherein the at least one monoamine functionalized polyalkyleneoxide is methoxypolyethyleneglycolamine, methoxypolypropyleneglycolamine, methoxypoly(ethylene-co-propylene)glycolamine.
9. The polymer composition according to any of embodiments 1 to 8, wherein the at least one aromatic compound is selected from isatoic anhydride and naphthalic anhydride.
10. A method for preparing the polymer composition of any of embodiments 1 to 9 comprising the steps of
11. The method according to embodiment 10, wherein the step (ii) of mixing is carried out at a temperature in the range from 30° C. to 120° C. for a time period in the range from 0.5 h to 24 h.
12. A liquid composition in the form of a dispersion comprising
13. A coating composition comprising the liquid composition according to embodiment 12.
14. The coating composition according to embodiment 13 further comprising at least one additive selected from pigment pastes, binders, fillers, solvents, defoamers, neutralising agent, wetting agent, pigment dispersing agents, preservatives and water.
15. Use of the polymer composition according to any of embodiments 1 to 9 as a dispersant in a coating composition.
While the presently claimed invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the presently claimed invention.
The presently claimed invention is illustrated in detail by non-restrictive working examples which follow. More particularly, the test methods specified hereinafter are part of the general disclosure of the application and are not restricted to the specific working examples.
EFKA® 2550 defoamer for various water-based coating systems and pigment concentrates;
Hydropalat® WE 3370 fluorcarbon modified polyacrylate used as wetting agent; available from BASF Se.
Setaqua® 6801 waterborne acrylic copolymer dispersion suitable for OEM metal or plastic basecoats available from Allnex.
Jeffamine® M 2070 a relatively hydrophilic polyether monoamine of approximately 2000 molecular weight available from Huntsman.
The molecular weight (Mw) was determined according to DIN 55672-1.
The acid number was determined according to DIN 53402:1990-09.
The amine number was determined according to DIN 53176:2002-11.
The viscosity was determined by analogy to DIN 53019-1:2008-09, using a Thermo Haake RheoStress® 600 equipment under the CR mode at 22° C. and a shear rate of 1 sec−1 (Spindle CP50).
Jetness (blackness, My) was determined according to DIN 55979.
Intermediate A1 was prepared according to EP1861429B1 Example A3 (Poly(n-BA-M PEGA-b-4-VP).
Intermediate A2 was prepared according to WO08006723A1 Example A15 ((Poly(n-BA-MPEGA-b-4-DMAPMA).
A 300 mL four-necked flask equipped with a stirrer, a thermometer and maintained under nitrogen atmosphere, was charged with 150 g Jeffamine® M 2070 (MW of 2000 g/mol), 11.6 g isatoic anhydride with 0.2 g 1,4-diazabicyclo[2.2.2]octane (DABCO). The reaction mixture was stirred at room temperature for 1 h and then the reaction temperature was slowly increased to 100° C. and followed by stirring under these conditions for 5 h. Intermediate B1 was obtained as a brownish liquid having an amine number of 23 mg KOH/g.
A 300 mL four-necked flask equipped with a stirrer, a thermometer and maintained under nitrogen atmosphere, was charged with 150 g Jeffamine® M 2070 (MW of 2000 g/mol), 14.1 g 1,8-naphthalic anhydride. The reaction mixture was stirred at 100° C. for 5 h. Intermediate
B2 was obtained as a brownish liquid having an acid number of 20 mg KOH/g.
A 300 mL four-necked flask equipped with a stirrer, a thermometer and maintained under nitrogen atmosphere, was charged with 150 g Jeffamine® M 2070 (MW of 2000 g/mol), 14.1 g 1,8-naphthalic anhydride. The reaction mixture was stirred at 100° C. for 2 h. Then, the reaction mixture was heated to 150° C. under vacuum for 5 h. Intermediate B3 was obtained as a brownish liquid having an acid number of 2 mg KOH/g.
The dispersants 1-6 were prepared by blending intermediates A and B mentioned in Table 1 in specified amounts at 80° C. under stirring for 3 h.
In order to test the dispersion effect of the obtained samples, resin free pigment concentrates (millbase) were prepared according to the Formulation 1. The millbase was dispersed in Scandex Shaker for 4 h with the help of glass beads. Afterwards the millbase was filtered and stored at room temperature overnight.
The performance of the dispersants was generally very good with low millbase viscosity (Table 2).
The paint was prepared by mix of 2.0 g millbase into 8.0 g let-down system (Formulation 2) via Dispermat® for 2 min at 2000 rpm.
The paint was applied on polyester film with a 75 μm film thickness. The wet films stand at room temperature for 30 min, followed by 90° C. for 30 min.
The dried film was generally very good with satisfactory results (Table 3).
| Number | Date | Country | Kind |
|---|---|---|---|
| 21165178.1 | Mar 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/057569 | 3/23/2022 | WO |
