Patent Publication Number: US-2023141337-A1

Title: Comb polymer and use thereof as dispersing agent

Description:
The invention relates to a comb polymer, a process for preparing the comb polymer, a composition comprising solid particles and the comb polymer, and to the use of the comb polymer as a wetting and/or dispersing agent for solid particles. 
     WO 2005/113677 A1 describes comb-like polyether alkanolamines in inks. The comb-like polyether alkanolamines are used as water-soluble dispersant for pigments in ink compositions. In one embodiment, the comb-like polyether alkanolamines have secondary amine end groups. In an alternative embodiment, the comb-like polyether alkanolamines have epoxy end groups. Secondary amine groups and epoxy groups are capable of various chemical reactions. In curable compositions the dispersants known from this document may interfere with reactive groups present in curable binder components or crosslinkers. This may impair the performance of the compositions as well as the dispersing ability of the polyether alkanolamines. It also limits the suitability of the known polyether alkanolamines as universal dispersants for a large variety of pigmented compositions. 
     There is an ongoing need for polymeric dispersing agents which are suitable for a variety of pigmented compositions which show a good ability for wetting and dispersing pigments and fillers. The polymeric dispersing agents should be suitable for different types of pigments, for example organic and inorganic pigments, as well as carbon black. Examples of pigmented compositions include coating compositions, inks, pigment pastes, pigmented master batches, and pigmented polymer compositions. 
     The invention provides a comb polymer having repeating units of at least one of the structures of formulae (I) to (IV) 
     
       
         
         
             
             
         
       
         
         
           
             wherein R 1  represents a polyoxyalkylene group and A represents an organic group, 
             and wherein the comb polymer has end groups of the general formula (V) 
           
         
       
    
     
       
         
         
             
             
         
       
     
     wherein R 2  and R 3  independent of each other are selected from a) organic groups having 1 to 24 carbon atoms and b) R 1 . 
     The comb polymer of the invention is suitable as dispersing agent for a variety of pigmented compositions. The comb polymer generally exhibits a good ability for wetting and dispersing pigments and fillers and is suitable for different types of pigments, for example organic and inorganic pigments, as well as carbon black. The comb polymer is very suitable for use in different pigmented compositions, for example coating compositions, inks, pigment pastes, pigmented master batches, and pigmented polymer compositions. In particular, the comb polymer of the invention provides pigmented compositions having a high transparency, a low viscosity, and good pigment stabilization. For compositions containing carbon black a high jetness is achieved. Jetness means that the surface appearance of the hue has a bluish undertone, which elevates the visual blackness. Generally, a decrease in mean particle size of carbon black pigments leads to an increase in jetness. The jetness can be quantified by the color independent blackness value as the MY value according to DIN 55979. The comb polymer can be used in water-based compositions as well as in non-aqueous compositions. 
     The polymer of the invention is a comb polymer. Comb polymers consists of an essentially linear main polymer chain, with two or more branch points where pendant polymeric side chains are linked to the main polymer chain. The pendant polymeric side chains are linear or essentially linear. 
     The comb polymer has repeating units of at least the structures of formulae (I) to (IV), as described above. 
     The group R 1  in formula (I) to (IV) represents a polyoxyalkylene group. The R 1  groups form the pending polymer chains in the comb polymer. 
     It is preferred that R 1  comprises repeating units from at least one of oxyethylene, oxypropylene, and oxybutylene. It is particularly preferred that R 1  comprises oxyethylene and oxypropylene repeating units. In some embodiments, the repeating units in R 1  consist of oxyethylene and oxypropylene. If more than one type of oxyalkylene repeating unit is present in R 1 , the different types of oxyalkylene repeating units may be arranged in random order. Alternatively, the different types of oxyalkylene units may be arranged in the form of two or more blocks. The groups R 1  in individual repeating units of a comb polymer may have the same or a different composition, number of repeating units, and repeating unit distribution. Generally, R 1  comprises from 10 to 80 oxyalkylene groups, preferably from 15 to 60 oxyalkylene groups. 
     In preferred embodiments, the group R 1  is terminated by a hydrocarbyl group having 1 to 10 carbon atoms. it is more preferred that R 1  is terminated by a lower alkyl group, in particular a methyl-, ethyl-, propyl- or butyl group. Preferably, the terminating hydrocarbyl group is linked to the polyoxyalkylene part of R 1  via an ether linkage. 
     In alternative embodiments, the group R 1  is terminated by a hydroxyl group. 
     Generally, the groups R 2  and R 3  in general formula (V) do not contain primary or secondary amine groups, and they do not contain epoxide groups. 
     In preferred embodiments, at least one of R 2  and R 3  is a hydroxyalkyl group having 2 to 4 carbon atoms, for example a hydroxyethyl group. In some embodiments, one or both of the groups R 2  and R 3  represent a hydrocarbyl group having 1 to 12 carbon atoms, for example an alkyl group having 2 to 8 carbon atoms. In alternative embodiments, one of the groups R 2  and R 3  represents a group R 1  as defined above. 
     In a further preferred embodiment R 2  is equal to R 1  and R 3  is a group of formula (VI) 
     
       
         
         
             
             
         
       
     
     wherein R 4  is an organic group having 2 to 20 carbon atoms and selected from hydrocarbyl groups, ether groups and ester groups. 
     The group A in formulae (I) to (IV) represents an organic group. In some embodiments, the group A represents a hydrocarbyl group, for example a hydrocarbyl group having 4 to 40 carbon atoms. Preferably, the hydrocarbyl group has 4 to 20 carbon atoms. The hydrocarbyl group can be a linear or cyclic aliphatic hydrocarbyl group, an aromatic hydrocarbyl group, or an alkylaromatic hydrocarbyl group. In preferred embodiments, A represents an organic group comprising at least one ether group. In further preferred embodiments, A consists of ether groups and hydrocarbyl groups. In this case, the hydrocarbyl groups are generally defined as above. 
     The comb polymer of the invention comprises tertiary amine groups. In one embodiment, at least a part of the tertiary amino groups of the repeating units of the structures of formulae (I) to (IV) are present in salt form. All or some of the tertiary amine groups may be converted to salts. The tertiary amino groups may, for example, be converted to corresponding ammonium salts by reaction with acids such as carboxylic acids, carboxylic acid derivatives, for example carbonyl halides, or phosphoric acids and acidic esters thereof. 
     In a further embodiment, at least a part of the tertiary amino groups of the repeating units of the structures of formulae (I) to (IV) have been converted to quaternary ammonium groups. 
     The quaternary ammonium groups are suitably prepared by quaternization of the tertiary amine group of the repeating units of formulae (I) to (IV) with suitable quaternization agents. Examples of suitable quaternization agents are alkyl halides, benzyl halides, dialkylsulfates, alkyl tosylates, and epoxides. The quaternary ammonium groups generally have anions as counter ions. In preferred embodiments, the counter ions comprise at least one of chloride, bromide, iodide, tosylate, methylsulfate, and carboxylate. 
     Conversion to salts or quaternization can, for example, increase or adjust the compatibility of the comb polymer with respect to particular media or affect the interaction with solid particles such as pigments and/or fillers. 
     In the comb polymer, the sum of the repeating units of the structures of formulae (I), (II), (Ill), and (IV) is generally in the range of 2 to 25, preferably in the range of 4 to 20, more preferably in the range of 3 to 10. 
     The comb copolymer generally has a number average molecular weight in the range of 4000 to 100000 g/mol, preferably in the range 6000 to 50000 g/mol. The number-average molecular weight M n  and the weight-average molecular weight M w  can be determined in accordance with DIN 55672-1:2007-08 by means of gel permeation chromatography using tetrahydrofuran containing 1% by volume of dibutylamine as eluent and polystyrene as calibration standard. 
     It is preferred that the comb polymer of the invention has a low content of epoxide groups or is essentially free or free of epoxide groups. Generally, the comb polymer has an epoxide equivalent weight of at least 10000 g/mol, preferably at least 20000 g/mol, or even 50000 g/mol or higher. When the comb polymer is entirely free of epoxide groups, the epoxide equivalent weight is infinite. The epoxide equivalent weight can be determined by titration, for example as described in standard method ASTM D 1652-97. 
     Is further preferred that the comb polymer of the invention has low content of primary and secondary amine groups, or is essentially free of free of such groups. Generally, the comb polymer has a combined content of primary and secondary amine groups of at most 10 mg KOH/g, preferably at most 5 mg KOH/g, or at most 1 mg KOH/g. When the comb polymer is entirely free of primary and secondary amine groups, their combined content is 0 mg KOH/g. The content of primary and secondary amine groups, in the presence of tertiary amines groups, can be determined as described in standard method ISO 9702:1996. 
     The invention further relates to a process for preparing the comb polymer of the invention. The process comprises reacting
         a) a diepoxide and a primary monoamine of the formula R 1 —NH 2 , wherein the molar ratio of epoxide groups to amine active hydrogens of the primary monoamine is not equal to 1:1, and   b) a monoepoxide of the formula (VII)       

     
       
         
         
             
             
         
       
         
         
           
             
               
                 if a molar excess of amine active hydrogens is employed in a), or a secondary amine of the formula HNR 2 R 3 , if a molar excess epoxide groups is employed in a),
 
wherein R 1 , R 2 , R 3 , and R 4  are defined as above.
 
               
             
           
         
       
    
     The reaction of epoxides and amines can be carried out at ambient temperature or at elevated temperature, for example on the range of 20° C. to 200° C. If so desired, the reaction may be carried out in the presence of a catalyst, for example a basic catalyst. 
     Suitable diepoxides to be used in the process include are compounds having two epoxide groups. Preferred diepoxides are diglycidylethers of aliphatic and aromatic alcohols. Such diglycidylethers are commercially available. They are suitably formed by reacting reactive phenols or alcohols with epichlorohydrin. Alternatively, diepoxides can be prepared by epoxidation reaction of compounds having two olefinic double bonds. Preferably the diepoxides used in the present invention are selected from the group consisting of glycidyl ethers, like bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, oligomeric and polymeric diglycidylethers based on bisphenol A and/or Bisphenol F and/or hydrogenated bisphenol A and/or hydrogenated Bisphenol F, 1,3-propane-, 1,4-butane- or 1,6-hexanediol-diglycidyl ether and polyalkylenoxide glycidyl ether; glycidyl esters, like hexahydrophthalic acid diglycidyl ester; cycloaliphatic epoxides, like 3,4-epoxycyclohexyl-epoxyethane or 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carboxylate. 
     Preferred examples of diepoxides are those based on bisphenol A, bisphenol F, or aliphatic and cycloaliphatic diols and epichlorohydrin, having a molecular weight between 300 and 5000 g/mol. 
     Suitable monoamines R 1 —NH 2  are commercially available from Huntsman under the trade designation Jeffamine® M. Specific commercials products include Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2005, Jeffamine® M-2070, Jeffamine® M-2095, and Jeffamine® M-3085. Other suitable monoamines are also available from Huntsman under the trade designation Surfonamine®. 
     As mentioned above, the diepoxide and the primary monoamine of the formula R 1 —NH 2 , are employed in amounts that the molar ratio of epoxide groups to amine active hydrogens of the primary monoamine is not equal to 1:1. 
     In one embodiment, a molar excess of diepoxide based epoxide groups over amine active hydrogens of the primary monoamine is used. In this case, the molar ratio of ratio of epoxide groups to amine active hydrogens of the primary monoamine generally is in the range of 1.00:0.95 to 1.00:0.60, preferably 1.0:0.90 to 1.0:0.70. 
     If a molar excess of epoxide groups over amine active hydrogens of the primary monoamine is used, a secondary amine of the formula HNR 2 R 3  is employed as well. Generally, the secondary amine is employed in an amount sufficient to ensure that the comb polymer is free or essentially free of epoxide groups. Examples of suitable secondary amines are dialkylamines, such as dimethyl amine, diethyl amine, di-n-propyl amine, di-iso-propyl amine, di-n-butyl amine, di-iso-butyl amine, diamyl amine, diisoamyl amine, di-n-hexyl amine, di-n-heptyl amine, di-n-octyl amine, dinonyl amine, didodecyl amine, di(2-ethylhexyl) amine, didoceyl amine, dicyclohexyl amine, diphenyl amine, dibenzyl amine, diallyl amine, piperidine, morpholine, methyl ethyl amine, methyl propyl amine, ethyl hexyl amine, or butyl octyl amine. 
     Preferred secondary amines are alkanolamines, for example diethanol amine, dipropanol amine, ethyl ethanol amine, methyl ethanol amine, ethyl propanol amine, and the like. 
     In some embodiments, the secondary amine may have a one or more tertiary amine groups. 
     Examples of such compounds are N 1 ,N 1 ,N 3 -trimethyl-1,3-propanediamine, N 1 ,N 1 -diethyl-N 3 -methyl-1,3-propanediamine, N 1 ,N 1 -diethyl-N 3 -methyl-1,3-propanediamine, N 1 ,N 1 -dimethyl-N 3 -propyl-1,3-butanediamine, N 3 [3-(dimethylamino)propyl]-N 1 ,N 1 -dimethyl-1,3-propanediamine, and N 3 -[3-(diethylamino)propyl]-N 1 ,N 1 -diethyl-1,3-propanediamine. 
     In an alternative embodiment, a molar excess of amine active hydrogens of the primary monoamine over epoxide groups is used. In this case, the molar ratio of ratio of epoxide groups to amine active hydrogens of the primary monoamine generally is in the range of 0.95:1.00 to 0.60:1.00, preferably 0.70:1.0 to 0.90:1.0. 
     If a molar excess of amine active hydrogens of the primary monoamine over epoxide groups is used, a monoepoxide of the formula (VII) is employed as well. Generally, the monoepoxide is employed in an amount sufficient to ensure that the comb polymer is free or essentially free of primary and secondary amine groups. Examples of suitable monoepoxides include epoxidized olefins, glycidylethers of monoalcohols, and glycidylesters. Specific compounds include aliphatic, cycloaliphatic, aromatic and/or araliphatic glycidyl ether, glycidyl ester and olefin oxides like C1-C20-alkyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, naphthyl glycidyl ether, butyl glycidyl ether, p-tert.-butyl-phenyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, C12-C14-glycidyl ether, allyl glycidyl ether, 2,3-epoxypropylneodecanoate (Cardura® E 10, Resolution Performance Products), C4-C20-olefine oxides like 1,2-octene oxide, 1,2-nonene oxide, 1,2-undecene oxide, 1,2-dodecene oxide, 1,2-octadecene oxide, 4-methyl-1,2-pentene oxide, 1,2-butene oxide, propene oxide, ethylene oxide, styrene oxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide and/or 2-ethyl-1,2-butene oxide. 
     The reaction can be carried out in one or more reaction steps. 
     In one embodiment, the diepoxide and primary monoamine are mixed to have a molar excess of epoxide groups over amine active hydrogens of the primary monoamine, and the mixture is reacted in a first step until essentially all primary amine groups have been converted to tertiary amine groups, followed by a second step wherein a secondary amine is added and reaction is continued until essentially all epoxide groups have been consumed. Alternatively, the diepoxide, the primary monoamine, and the secondary amine may be combined and reacted in a single step to form the comb polymer of the invention. 
     In a different embodiment, the diepoxide and primary monoamine are mixed to have a molar excess of amine active hydrogens of the primary monoamine over epoxide groups, and the mixture is reacted in a first step until essentially all epoxide groups have reacted, followed by a second step wherein a monoepoxide is added and reaction is continued until essentially all amine groups have been converted to tertiary amine groups. Alternatively, the diepoxide, the primary monoamine, and the monoepoxide may be combined and reacted in a single step to form the comb polymer of the invention. 
     The comb polymer of the invention is very suitable as a wetting and/or dispersing agent for solid particles. Therefore, the invention also relates to a composition comprising solid particles and the comb polymer according to the invention. Preferred examples of solid particles are pigments and fillers. The invention further relates to the use of the comb polymer as a wetting and/or dispersing agent for solid particles. 
     Representative examples of solid particles include pigments, fillers, flame retardants, and fibers. 
     The pigments may be those known to a skilled person. The pigments may be organic pigments or inorganic pigments as well as carbon black. 
     Examples of suitable organic pigments include mono-, di-, tri- and polyazo pigments, oxazine, dioxazine, thiazine pigments, diketo pyrrolopyrroles, phthalocyanines, ultramarine and other metal complex pigments, indigoid pigments, diphenylmethane pigments, triarylmethane pigments, xanthene pigments, acridine pigments, quinacridone pigments, methine pigments, anthraquinone, pyranthrone, perylene pigments and other polycyclic carbonyl pigments. 
     When the solid particles to be dispersed are organic pigments, improved results have been obtained with comb polymers 
     In some embodiments, the pigments are carbon black pigments and/or pigments based on carbon black, such as graphite or carbon nanotubes. When carbon black is to be dispersed, improved results have been obtained with respect to viscosity reduction. Also an increase in transparency, a reduction of particle size and improvement of jetness indicate a better dispersion. 
     In a further embodiment, the pigments are inorganic pigments, such as zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithophones, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate, cobalt zincate, antimony oxide, antimony sulfide, chromium oxide, zinc chromate, mixed metal oxides based on nickel, bismuth, vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum (for example, nickel titanium yellow, bismuth vanadate molybdate yellow or chromium titanium yellow). 
     In some embodiments, the pigments include corrosion inhibiting pigments. Examples of suitable corrosion inhibiting pigments are those known in the art and include zinc oxide, phosphates, such as zinc phosphate, zinc powder, and platelet shaped pigments, such as iron oxide. 
     Inorganic pigments can 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 or fluorescent and phosphorescent pigments 
     Examples of powdery or fibrous fillers include those, which are composed of powdery or fibrous particles of alumina, aluminum hydroxide, silica, diatomaceous earth, siliceous earth, quartz, silica gel, talc, kaolin, mica, perlite, feldspar, slate flour, calcium sulfate, barium sulfate, calcium carbonate, calcite, dolomite, glass or carbon. 
     Solid particles include flame retardants, such as aluminum or magnesium hydroxide, and matting agents, such as silicas. 
     The weight ratio of comb polymer to solid particles is not particularly critical. For organic pigments, 10 to 50% by weight of comb polymer, calculated on the weight of the organic pigment, may suitably be employed. For inorganic pigments, 1 to 30% by weight of comb polymer, calculated on the weight of the inorganic pigment, may suitably be employed. 
     In case of very finely divided pigments, for example some carbon blacks, 30 to 90% by weight of comb polymer, calculated on the weight of the finely divided pigment, may be employed. 
     The composition can suitably be employed in areas wherein solid particles are dispersed in a composition, for example coatings, paints, plastics, pigment pastes, sealants, ceramics, cosmetics, adhesives, casting compounds, fillers, battery applications, gas and oilfield applications, spackling compounds, inks and printing inks, and flat panel displays. 
     The invention also relates to a process of dispersing solid particles, comprising the steps of 
     a) Mixing at least one type of solid particles, and the comb polymer of the invention in a dispersion medium, and 
     b) Exerting shear force to the mixture prepared in step a). 
     The process can be carried out in a conventional way of dispersing solid particles, as it is well known, for example in the industries concerned with coating compositions or casting compositions. The dispersion medium may be a liquid, for example an organic solvent or water. Alternatively, the dispersion medium may be a resin or polymer, for example a film forming binder. The resin or polymer may optionally be dissolved in a liquid diluent. 
     Examples of suitable resins or polymers include synthetic, semisynthetic or natural macromolecular substances, such as polyvinyl chloride, saturated or unsaturated polyesters, polyurethanes, polystyrene, polyacrylates, polyamides, epoxy resins, and polyolefins, such as polyethylene or polypropylene, cellulose nitrate, cellulose acetobutyrate, alkyd resins, and melamine resins. 
    
    
     EXAMPLES 
     Raw Materials Used: 
     Epikote 828 is an aromatic diepoxide from Hexion 
     Jeffamine M 2070 is a polyetheramine from Huntsman Corporation 
     DABCO is a catalyst from Air products 
     2,2′-Iminodiethanol supplied by BASF SE 
     Dibutylamine supplied by Sigma Aldrich 
     Dibenzylamine supplied by Sigma Aldrich 
     N-benzylmethylamine supplied by Sigma Aldrich 
     Epalloy 5001LC is an aliphatic diepoxide from Emerald Performance Materials 
     Grilonit RV 1814 is an C13/C15 alkyl glycidylether from EMS Griltech 
     Oxirane, 2-[(2-methylphenoxy)methyl]- is supplied by Dow 
     Termination with Secondary with Secondary Amine 
     Preparation Example 1 
     45 g Epikote 828 and 193 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until only two epoxide groups were detected per polymer by 1H-NMR (integrated). After two hours, 0.25 g DABCO were added as catalyst. Afterwards, 5 g 2,2′-Iminodiethanol are were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     Preparation Example 2 
     45 g Epikote 828 and 193 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until only two epoxide groups were detected per polymer by 1H-NMR (integrated). After two hours, 0.25 g DABCO were added as catalyst. Afterwards, 6 g dibutylamine were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     Preparation Example 3 
     45 g Epikote 828 and 193 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until only two epoxide groups were detected per polymer by 1H-NMR (integrated). After two hours, 0.25 g DABCO were added as catalyst. Afterwards, 5 g dibenzylamine were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     Preparation Example 4 
     45 g Epikote 828 and 193 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until only two epoxide groups were detected per polymer by 1H-NMR (integrated). After two hours, 0.25 g DABCO were added as catalyst. Afterwards, 6 g N-benzylmethylamine were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     Preparation Example 5 
     32 g Epalloy 5001LC and 124 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until only two epoxide groups were detected per polymer by 1H-NMR (integrated). After two hours, 0.15 g DABCO were added as catalyst. Afterwards, 3.2 g 2,2′-Iminodiethanol are were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     In preparation Examples 1 to 5 the molar ratio of epoxide groups to amine active hydrogens of the primary monoamine to the amine active hydrogens of the secondary amine was 10:8:2. 
     Termination with Monoepoxide 
     Preparation Example 6 
     30 g Epikote 828 and 193 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until no epoxide groups were detected per polymer by 1H-NMR (integrated). Afterwards, 4.5 g Grilonit RV 1814 were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     Preparation Example 7 
     30 g Epikote 828 and 193 g Jeffamin M 2070 were combined and stirred for 6 hours at 140° C. under N 2 -atmosphere until no epoxide groups were detected per polymer by 1H-NMR (integrated). Afterwards, 2.3 g Oxirane, 2-[(2-methylphenoxy)methyl]- were added and the reaction mixture was stirred for an additional 6 hours at 140° C. until no epoxide groups were detected by 1H-NMR. An amber, clear, viscous polymer was obtained. 
     All examples had the same ratio of epoxide groups belonging to the diepoxide to amine active hydrogens of the primary monoamine to epoxide groups belonging to the monoepoxide (8:10:2). 
     Comparative Preparation Examples 
     (1) According to patent EP 1 745 104 B1, preparation 7 (Huntsman) 
     (2) Material described in EP 1 486 524 B1 was prepared by combining 30 g Epikote 828, 193 g Jeffamin M 2070 and 0.2 g DABCO. The reactants were stirred for 12 hours at 140° C. under N2-atmosphere until no epoxide groups were detected per polymer by 1H-NMR (integrated). An amber, clear, viscous polymer was obtained. The ratio of epoxide groups to amine active hydrogens was 10:12. 
     Application Examples 
     To evaluate the effectiveness of the inventive polymers as pigment dispersants, they were tested in different coating compositions. 
     Application Example 1: Laropal Dispersion 
     As first step, pigment concentrates with different pigments were made with an inorganic pigment (Bayferrox 130M) and a carbon black pigment (Special Black 4). The components shown in Table 1 were combined and dispersed in a Lau-Disperser with 1 mm glass beads to create the pigment concentrates (2 hours for Bayferrox 130M, 4 hours for Special Black 4). 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Composition of the pigment concentrates. Laropal A 81 is an  
               
               
                 aldehyde resin from BASF SE, GARAMITE 7305 is a  
               
               
                 clay-based rheology additive from BYK-Chemie GmbH, 
               
               
                 Bayferrox 130M is a micronized iron oxide red pigment  
               
               
                 from LANXESS, Special Black 4 is a carbon black  
               
               
                 pigment from Orion Engineered Carbon. 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 Pigment 
                 Pigment 
               
               
                   
                   
                 Concentrate 
                 Concentrate 
               
               
                   
                 Raw material 
                 130M 
                 Sp. Black 4 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Laropal A 81 60% 
                 12.50 
                 10.60 
               
               
                   
                 2-Propanol, 1- 
                 22.60 
                 27.40 
               
               
                   
                 methoxy-, acetate 
                   
                   
               
               
                   
                 Inventive or 
                 4.50 
                 4.00 
               
               
                   
                 comparative polymers 
                   
                   
               
               
                   
                 GARAMITE 7305 
                 0.40 
                   
               
               
                   
                 Bayferrox 130M 
                 60.00 
                   
               
               
                   
                 Special Black 4 
                   
                 8.00 
               
               
                   
                   
                 100.00 
                 50.00 
               
               
                   
                   
               
            
           
         
       
     
     The viscosities of the pigment concentrates were measured one day after grinding. The viscosities and the particle size of the pigment concentrates using the polymers of preparation examples 1 and 5 (present invention) and comparative example 1 are shown in Table 2 below. The viscosity was measured with an Anton Paar rheometer ((25 mm 0, 1°, 23° C.) at high shear rates. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Viscosities of samples of pigment concentrate  
               
               
                 Bayferrox 130M for high (100 1/s) shear rates. 
               
            
           
           
               
               
               
            
               
                   
                   
                 mPa s at 100 1/s— 
               
               
                   
                   
                 after 1 d RT 
               
               
                   
                   
                 Pigment 
               
               
                   
                   
                 Concentrate 
               
               
                   
                 Polymer sample 
                 130M 
               
               
                   
                   
               
               
                   
                 Comp. Example 1 
                 431.4 
               
               
                   
                 Example 1 
                 282.4 
               
               
                   
                 Example 5 
                 148.8 
               
               
                   
                   
               
            
           
         
       
     
     The inventive samples showed a better viscosity reduction than the comparative example for the pigment concentrate with the inorganic exemplary pigment. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Viscosities of samples of pigment concentrates  
               
               
                 Special Black 4 for high (100 1/s) shear rates. 
               
            
           
           
               
               
               
            
               
                   
                   
                 mPa s at 100 
               
               
                   
                   
                 1/s—after 1 d 
               
               
                   
                   
                 RT 
               
               
                   
                   
                 Pigment 
               
               
                   
                   
                 Concentrate 
               
               
                   
                 Polymer sample 
                 Sp. Black 4 
               
               
                   
                   
               
               
                   
                 Comparative Example 1 
                 42.7 
               
               
                   
                 Example 1 
                 29.8 
               
               
                   
                 Example 5 
                 22.6 
               
               
                   
                   
               
            
           
         
       
     
     The viscosity for carbon black also improved with the inventive products indicating that the dispersion ability improved also for the exemplary organic pigment. 
     Letdown 
     To form the final coating composition, the pigment concentrate was combined with the letdown and hardener with the composition shown in table 4 and 5. The mixing ratio of the three components is shown in table 6. After application on the panel, the coating is cured for 30 min at 60° C. after 60 minutes flash off time. 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Composition of hardener 
               
            
           
           
               
               
               
            
               
                   
                 Component 
                 Ratio 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Desmodur N75 
                 25.00 
               
               
                   
                 Butyl acetate 
                 8.70 
               
               
                   
                 Solvent naphtha 
                 8.80 
               
               
                   
                 (petroleum), light arom. 
                   
               
               
                   
                 2-Propanol, 1-methoxy-, 
                 2.50 
               
               
                   
                 acetate 
                   
               
               
                   
                 Xylene 
                 5.00 
               
               
                   
                   
                 50.00 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Composition of letdown 
               
            
           
           
               
               
               
            
               
                   
                 Component 
                 Ratio 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Macrynal SM 510 
                 75.00 
               
               
                   
                 Xylol 
                 6.60 
               
               
                   
                 Solvent Naphtha 
                 5.00 
               
               
                   
                 Butyl acetate 
                 8.00 
               
               
                   
                 2-Propanol, 1- 
                 5.00 
               
               
                   
                 methoxy-, acetate 
                   
               
               
                   
                 BYK-066N 
                 0.30 
               
               
                   
                 BYK-306 
                 0.10 
               
               
                   
                   
                 100.00 
               
               
                   
                   
               
            
           
         
       
     
     Macrynal SM 510 is an acrylic resin from Allnex, BYK-066N is a silicone defoamer from BYK-Chemie GmbH, BYK-306 is a surface-active additive from BYK-Chemie GmbH, Desmodur N75 is an isocyanate hardener from Covestro AG. 
     Mixing Ratio 
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Mixing ratio of Pigment concentrate, letdown and hardener. 
               
            
           
           
               
               
               
               
               
               
            
               
                 Pigment 
                   
                   
                   
                   
                   
               
               
                 Concentrate 
                 Let-Down 
                 130M 
                 SBlack 4 
                 Hardener 
                 Sum 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 130M 
                 17.3 
                 4.0 
                   
                 8.7 
                 30.0 
               
               
                 Sp. Black 4 
                 18.1 
                   
                 2.8 
                 9.1 
                 30.0 
               
               
                   
               
            
           
         
       
     
     Results 
     To evaluate the efficiency of dispersion of the pigment concentrates, the transparency was assessed and haze as well as gloss were measured. The transparency was assessed by visual valuation. The coating was applied on a PET-foil (50 μm wire bar) and held against a light source. Haze and gloss of the coating was measured on the same foil with a BYK haze-gard for the haze measurement and the BYK-micro-haze plus for the gloss (20° angle). The results are summarized in table 7. 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Results of transparency, transmission, haze and gloss  
               
               
                 measurement for Special Black 4 coating. 
               
            
           
           
               
               
               
               
            
               
                   
                 Transparency 
                 Haze 
                 Gloss 
               
               
                 Coating sample 
                 Sp. Black 4 
                 Sp. Black 4 
                 Sp. Black 4 
               
               
                   
               
               
                 Comparative Example 1 
                 3 
                 19 
                 85 
               
               
                 Example 1 
                 1-2 
                 16 
                 86 
               
               
                 Example 5 
                 1-2 
                 16 
                 86 
               
               
                   
               
            
           
         
       
     
     The transparency improved significantly with the inventive products, showing that the dispersion quality increased. The haze of the coating is low while the gloss is good in all cases. 
     To evaluate the efficiency of dispersion of the pigment concentrate 130M, a rub out test was performed. After storage, the paint is applied on a contrast test chart by use of a frame applicator (100 μm wire bar). The Rub-up-test is carried out by rubbing a finger on the surface of the paint (about ⅓ of the applied area) until there is a certain resistance against the rubbing and the color difference between the rubbed and the untreated area reaches the highest value and stays constant. After drying, an evaluation of the color difference is performed with a Spectro Guide Sphere Gloss (20° Angle). 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Results of Rub-Out (Delta-E,  
               
               
                 b*-value and Gloss) for Bayferrox 130M coating 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 Delta-E 
                 Gloss 
               
               
                   
                 Coating sample 
                 Bayferrox 130M 
                 Bayferrox 130M 
               
               
                   
                   
               
               
                   
                 Comparative Example 1 
                 1.13 
                 93 
               
               
                   
                 Example 1 
                 0.96 
                 93 
               
               
                   
                 Example 5 
                 0.68 
                 93 
               
               
                   
                   
               
            
           
         
       
     
     The dispersion quality and thus the Delta-E values of the Rub-Out improved with the inventive products. Especially Example 5 shows a low delta-e value and thus a good dispersion and stabilization of the pigment. The gloss is good in all cases. 
     Application Example 2: Epoxy Coating System 
     For the second type of coating composition, all liquid components (Epikote 1001 X75, exemplary polymer and BYK-052 N) were combined in a pot and located under a grinding vessel (4 cm tooth plate). The solid components (Bayferrox 130M, Blanc Fixe N and GARAMITE 7305) were stirred in with a low mixing rate. After complete addition, the components were dispersed for 30 minutes at 50° C. and 8500 rpm. Afterwards, the solvent mixture was added. The curing agent was added before application of the coating composition. 
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Coating composition of epoxy coating example. Epikote 1001  
               
               
                 X75 is a solid epoxy resin from Hexion, BYK-052 N is a  
               
               
                 defoamer from BYK-Chemie GmbH, Blanc Fixe N is a 
               
               
                 barium sulfate whit pigment from Solvay, MIBK is a solvent  
               
               
                 from Eastman, iso-Butanol is a solvent from Dow, Epikure  
               
               
                 3115 X70 is a polyamide based curing agent from Hexion. 
               
            
           
           
               
               
               
            
               
                   
                   
                 2-pack- 
               
               
                   
                   
                 Epoxy 
               
               
                   
                 Raw materials 
                 Coating 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Epikote 1001 X75 
                 128.00 
               
               
                   
                 Inventive or comparative 
                 1.80 
               
               
                   
                 polymers 
                   
               
               
                   
                 BYK-052 N 
                 1.00 
               
               
                   
                 Bayferrox 130M 
                 15.00 
               
               
                   
                 Blanc Fixe N 
                 110.60 
               
               
                   
                 GARAMITE 7305 
                 1.60 
               
               
                   
                 Grinding vessel, 50° C., 
                   
               
               
                   
                 30 min, 8500 rpm, 4 cm- 
                   
               
               
                   
                 Tooth plate 
                   
               
               
                   
                 MIBK/iso-BuOH 7:3 
                 42.00 
               
               
                   
                   
                 300.00 
               
               
                   
                 Epikure 3115 X70 
                 45.00 
               
               
                   
                   
                 345.00 
               
               
                   
                   
               
            
           
         
       
     
     Viscosity 
     The viscosities of the coating composition without the curing agent using dispersant examples 1, 5 (present invention) and comparative examples 1 and 2 are shown in Table 10 below. The viscosity was measured with an Anton Paar rheometer ((25 mm 0, 1°, 23° C.) at different shear rates. The measurement was repeated after 7 d and the quotient of the viscosities for a shear rate 100 1/s recorded as storage index. 
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Viscosities of samples for high (100 1/s), medium (10 1/s)  
               
               
                 and low (1 1/s) shear rates. 
               
            
           
           
               
               
               
               
               
            
               
                   
                 mPa s at 1 
                 mPa s at 10 
                 mPa s at 100 
                 Storage 
               
               
                   
                 1/s—after 
                 1/s—after 
                 1/s—after  
                 Index at  
               
               
                 Sample 
                 1 d RT 
                 1 d RT 
                 1 d RT 
                 100 1/s 
               
               
                   
               
               
                 Comparative  
                 2869 
                 1467 
                 1037 
                 1.13 
               
               
                 Example 1 
                   
                   
                   
                   
               
               
                 Comparative  
                 2564 
                 2027 
                 1734 
                 0.86 
               
               
                 Example 2 
                   
                   
                   
                   
               
               
                 Example 1 
                 2156 
                 1708 
                 1465 
                 1.04 
               
               
                 Example 5 
                 1658 
                 1295 
                 1084 
                 1.08 
               
               
                   
               
            
           
         
       
     
     The viscosity of the inventive examples is lower for low shear rates. That leads to a better handling even with “bad” grinding conditions. The storage stability of the coating is furthermore enhanced which is reflected by the storage index. The same tendencies are found for low shear rates. 
     To evaluate the efficiency of dispersion of the pigment concentrate 130M, a rub out test was performed. After storage, the paint is applied on a contrast test chart by use of a frame applicator (100 μm wire bar). The Rub-Out-test is carried out by rubbing a finger on the surface of the paint (about ⅓ of the applied area) until there is a certain resistance against the rubbing and the color difference between the rubbed and the untreated area reaches the highest value and stays constant. After drying, an evaluation of the color difference is performed with a Spectro Guide Sphere Gloss. 
     
       
         
           
               
             
               
                 TABLE 11 
               
             
            
               
                   
               
               
                 Results of Rub-Out for the epoxy coating. 
               
            
           
           
               
               
               
            
               
                   
                 Sample 
                 Delta-E 
               
               
                   
                   
               
               
                   
                 Comparative Example 1 
                 1.02 
               
               
                   
                 Comparative Example 2 
                 0.58 
               
               
                   
                 Example 1 
                 0.54 
               
               
                   
                 Example 5 
                 0.51 
               
               
                   
                   
               
            
           
         
       
     
     The Delta-E values show that the Rub-Out and thus the dispersion efficiency is improved with the inventive polymers. 
     Application Example 3: Aqueous Ink 
     Water, biocide, defoamer and inventive or comparative polymer were combined and dispersed in a Lau-Disperser with 1 mm glass beads for 16 hours to prepare pigment concentrates. 
     
       
         
           
               
             
               
                 TABLE 13 
               
             
            
               
                   
               
               
                 Composition of the pigment concentrate for aqueous inks.  
               
               
                 Acticide MBS is a biocide from Lanxess, BYK-019 is a  
               
               
                 defoamer from BYK-Chemie GmbH, Emperor 1800 is a 
               
               
                 carbon black pigment from the Cabot Corporation. 
               
            
           
           
               
               
               
            
               
                   
                 Component 
                 Pigment Concentrate 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Water 
                 37.25 
               
               
                   
                 Inventive or comparative polymers 
                 5.00 
               
               
                   
                 Acticide MBS 
                 0.05 
               
               
                   
                 BYK-019 
                 0.20 
               
               
                   
                 Emperor 1800 
                 7.50 
               
               
                   
                   
                 50.00 
               
               
                   
                   
               
            
           
         
       
     
     The viscosities and the particle size of the pigment concentrates using dispersant examples 1, 2, 3, 4, 6, 7 (present invention) and comparative example 2 are shown in Table 14 below. The viscosity was measured with an Anton Paar rheometer (measurement system CP 50, T=25° C.) at a constant shear rate of 100 s −1 . The particle size of the pigment concentrates was measured with a NanoPlus DLS particle analyzer micromeritics). For this purpose 0.05 g of the pigment concentrate was diluted with 12.5 g water. 
     
       
         
           
               
             
               
                 TABLE 14 
               
             
            
               
                   
               
               
                 Viscosity and Particle Size of the pigment concentrate. 
               
            
           
           
               
               
               
            
               
                   
                   
                 Particle 
               
               
                   
                 Viscosity 
                 size 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 after 
                   
                 after 
               
               
                   
                 initial 
                 storage 
                 Storage 
                 storage 
               
               
                   
                 mPas 
                 mPas 
                 Index 
                 D50 [nm] 
               
               
                   
               
               
                 Comparative Example 2 
                 14.3 
                 12.4 
                 0.87 
                 62 
               
               
                 Example 1 
                 11.0 
                 10.8 
                 0.98 
                 59 
               
               
                 Example 2 
                 12.1 
                 11.5 
                 0.95 
                 60 
               
               
                 Example 3 
                 11.5 
                 11.1 
                 0.97 
                 59 
               
               
                 Example 4 
                 11.5 
                 10.9 
                 0.95 
                 56 
               
               
                 Example 6 
                 12.7 
                 12.7 
                 1.00 
                 60 
               
               
                 Example 7 
                 10.3 
                  9.9 
                 0.96 
                 62 
               
               
                   
               
            
           
         
       
     
     As can be seen, the polymer of the invention is much more effective at dispersing carbon black than the comparative example, as reflected by a lower viscosity. Furthermore, the storage stability improved significantly with the inventive products even without having a resin in the pigment paste. The particle size is comparable or better in most cases. 
     Application Example 4: Aqueous Carbon Black Dispersion 
     For the pigment concentrate, the raw materials shown in table 15 are mixed while stirring and the pH adjusted to 8.2-8.5 with Dimethylethylamine (10% solution in water) before grinding. The mixture is ground in a LAU Disperser DAS 200 for 4 hours with glass beads (1.0-1.2 mm) ratio=1:1 (by weight). After grinding, the pH is checked and if needed again adjusted to 8.2-8.5 with Dimethylethylamine (10% solution in water). 
     
       
         
           
               
             
               
                 TABLE 15 
               
             
            
               
                   
               
               
                 Composition of pigment concentrate. BYK-011 is a  
               
               
                 defoamer from BYK-Chemie GmbH, Raven 5000  
               
               
                 UIII is a carbon black pigment from Birla Carbon. 
               
            
           
           
               
               
               
            
               
                   
                   
                 [%] 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Deionized water 
                 82.2 
               
               
                   
                 Inventive or 
                 7.0 
               
               
                   
                 comparative polymers 
                   
               
               
                   
                 BYK-011 
                 0.8 
               
               
                   
                 Raven 5000 UIII 
                 10.0 
               
               
                   
                   
                 100.0 
               
               
                   
                   
               
            
           
         
       
     
     The letdown is prepared by combining the raw materials shown in table 16 while stirring. The pigment concentrate is added to the letdown and the viscosity is adjusted to the spray out viscosity with demineralized water (˜700 mPa*s Brookfield Viscometer at 50 rpm). The mixing ratio of pigment concentrate and letdown is shown in table 17. 
     
       
         
           
               
             
               
                 TABLE 16 
               
             
            
               
                   
               
               
                 Composition of letdown. Setaqua 6801 is an acrylic binder  
               
               
                 from Allnex, Setaqua 6802 is an acrylic binder from Allnex,  
               
               
                 BYK-028 is a defoamer from BYK-Chemie GmbH, BYK- 
               
               
                 348 is a silicone surfactant from BYK-Chemie GmbH,  
               
               
                 BYK-425 is a rheology additive from BYK-Chemie GmbH. 
               
            
           
           
               
               
               
            
               
                   
                 Let-down 
                 [%] 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Setaqua 6801 
                 23.8 
               
               
                   
                 Setaqua 6802 
                 44.9 
               
               
                   
                 BYK-028 
                 0.6 
               
               
                   
                 Dimethylethylamine 
                 2.0 
               
               
                   
                 10% in water 
                   
               
               
                   
                 Deionized water 
                 13.5 
               
               
                   
                 Butylglykol 
                 5.7 
               
               
                   
                 BYK-348 
                 0.5 
               
               
                   
                 BYK-425 
                 9.0 
               
               
                   
                 5% in water 
                   
               
               
                   
                   
                 100.0 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 17 
               
               
                   
                   
               
               
                   
                   
                 [%] 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Pigment Concentrate 
                 13.3 
               
               
                   
                 Let-down 
                 86.7 
               
               
                   
                   
                 100.0 
               
               
                   
                   
               
            
           
         
       
     
     The base coat is applied by hand on coil-primed aluminum panels with a spray gun (HVLP 3000, 1.3 mm nozzle) at 2 bar. The panel is cured by 30 min flash off at RT. 
     To evaluate the quality of dispersion, the jetness of the base coat was measured with a BYK-Gardner spectro guide 45/0. 
     
       
         
           
               
               
               
               
               
             
               
                   
                   
               
               
                   
                   
                 My 
                 dM 
                 Mc 
               
               
                   
                   
               
             
            
               
                   
                 Comparative Example 2 
                 259 
                 10 
                 269 
               
               
                   
                 Example 1 
                 264 
                 11 
                 275 
               
               
                   
                 Example 2 
                 264 
                 10 
                 274 
               
               
                   
                 Example 7 
                 266 
                  9 
                 274 
               
               
                   
                   
               
            
           
         
       
     
     It can be seen, that the Mc as well as the My values are higher for the inventive samples, indicating a good dispersion. The Undertone dM which is a indicator for the bluishness of the coating is good for all samples.