CN116745386A - Stable pigment dispersion composition - Google Patents

Stable pigment dispersion composition Download PDF

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Publication number
CN116745386A
CN116745386A CN202180084787.2A CN202180084787A CN116745386A CN 116745386 A CN116745386 A CN 116745386A CN 202180084787 A CN202180084787 A CN 202180084787A CN 116745386 A CN116745386 A CN 116745386A
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polyether
group
dispersant
amine
nucleophile
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E·库尔贝克
J·伯特
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Lubrizol Advanced Materials Inc
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Lubrizol Advanced Materials Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/52—Natural or synthetic resins or their salts

Abstract

The present invention provides a method of forming a pigment dispersion stable at elevated temperatures, wherein the dispersion comprises a pigment, a solvent, and a dispersant that is a salt of a polyether functionalized polyacid.

Description

Stable pigment dispersion composition
Technical Field
The disclosed technology relates to a pigment dispersion that is stable at elevated temperatures and can be used to prepare colored polymers.
Disclosure of Invention
The present invention relates to a method of forming a pigment dispersion stable at elevated temperatures comprising the steps of: (1) preparing a dispersion comprising (a) a solvent having a boiling temperature (T), wherein the solvent comprises or consists of ethylene glycol or an ethylene glycol oligomer, (b) a pigment, such as carbon black, and (c) a dispersant, (2) adding a material having a boiling point above the temperature (T), and (3) heating the dispersion at least to the boiling temperature (T) of the solvent.
The dispersant used in the present invention comprises salts of P and X. P is a polyether functionalized polyacid intermediate formed via the reaction of: (i) a maleic anhydride-containing polymer, (ii) a polyether mono-nucleophile C, and (iii) optionally, a non-polymeric mono-nucleophile D. X may be an alkali metal, alkaline earth metal, ammonia, amine or mixtures thereof.
In the dispersants used in the methods described herein, the maleic anhydride-containing polymer has the formula (A) n -(B) m -(E) q Wherein a is a maleic anhydride unit having the structure:
b is a styrene or substituted styrene unit having the structure:
wherein R is H or CH 3 Preferably H, R' is halogen, nitro (NO 2 ) A group, or optionally C containing an oxygen atom 1 To C 10 An alkyl group or aromatic group, E is 0 to 5, e.g., 1 to 5, or 0, and E is derived from a monounsaturated monomer containing 2 to 45 carbon atoms, which may optionally contain ethers, esters, amides, tertiary amines, acids, halogens, but not alcohols, primary amines, and secondary amines. In the maleic anhydride-containing polymer, n is 10 to 50, m is 10 to 150, q is 0 to 200, preferably 0, provided that the ratio of n to m is between 1:1 and 1:6.
Polyether mono nucleophile C comprises from 6 to 70 ethylene glycol repeat units and optionally comprises propylene glycol repeat units and/or butylene glycol repeat units, provided that at least 50% or at least 70% of all repeat units are ethylene glycol. Polyether mono nucleophile C contains a single alcohol, primary amine or secondary amine group. The non-polymeric mono nucleophile D is a linear or branched, saturated or unsaturated alkyl or aryl chain having from 1 to 22 carbon atoms and comprises a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D is substantially free of acid groups or free of acid groups.
10% to 100%, or 30% to 100%, or 50% to 100%, or 70% to 100% of the total moles of a in the polyether functionalized polyacid P is reacted with C; and 0% to 80%, or 0% to 50%, or 0% to 25% of the total moles of a is reacted with D; provided that after reaction of the repeating units a with C and D, at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90% of a must contain carboxylic acid groups and no more than 10%, or 0% to 5% of a units are still able to be in their anhydride form;
the invention also includes the use of the above dispersants to provide stable pigment dispersions at elevated temperatures.
Detailed Description
For simplicity of this disclosure, we will use brackets around "methyl" to indicate that the named molecules may optionally include methyl substituents, such as (meth) acrylic acid will be methacrylic acid and/or acrylic acid, and methyl (meth) acrylate will be methacrylate and/or acrylate. It is contemplated that the polyethers used herein may be random polyethers or block polyethers and are not intended to limit the polyethers to a single block or multiple blocks of any particular repeating unit. We will use the notation C (=o) -OH to represent any form of carboxylic acid, such as an acid form, a salt form, or an anhydride form if two carboxylic acids are physically adjacent and capable of forming an anhydride ring. If C (=o) -OH is adjacent to the nitrogen of the amide bond, we would also expect that it can be converted to C (=o) -as part of the imide. We will use the term "hydrocarbyl" to describe a hydrocarbon group from which one hydrogen is removed. Hydrocarbyl in this specification will mean similar hydrocarbons and may include up to one oxygen or nitrogen atom for every four carbon atoms in the group, but preferably only carbon and hydrogen atoms. Hydrocarbylene will mean a hydrocarbon from which two hydrogen atoms are removed. Hydrocarbylene groups will also optionally include up to one oxygen or nitrogen atom for every two carbon atoms in the group, but preferably only carbon and hydrogen atoms. For the avoidance of doubt, when counting carboxylic acid groups or carbonyl groups, we will count the anhydrides of dicarboxylic acids and imides for two carbonyl groups.
The present invention relates to a method of forming a pigment dispersion that is stable at elevated temperatures. The method comprises the following steps: (1) preparing a dispersion comprising (a) a solvent having a boiling temperature (T), wherein the solvent comprises or consists of ethylene glycol or an ethylene glycol oligomer, (b) a pigment, and (c) a dispersant, (2) adding a material having a boiling point above temperature (T), and (3) heating the dispersion to a temperature at least the boiling temperature (T) of the solvent. The invention also includes the use of dispersants to provide stable pigment dispersions at elevated temperatures.
The solvent used in the present invention comprises ethylene glycol or ethylene glycol oligomer, or a mixture thereof. In one embodiment, the solvent comprises, or consists of, ethylene glycol. In another embodiment, the solvent comprises or consists of ethylene glycol oligomers. In case the solvent comprises or consists of ethylene glycol oligomers, these oligomers may comprise 2 to 5 ethylene glycol repeating units. If the dispersion used in the present invention comprises one or more other co-solvents, these solvents may be selected from the group consisting of water, alkanols, alkanoic acids and alkanoic acid esters, and other solvents known to those skilled in the art. In one embodiment, the solvent will have a boiling temperature of at least 180 ℃, or at least 190 ℃, or at least 195 ℃, or at least 200 ℃. For example, ethylene glycol has a boiling temperature of 197 ℃. In embodiments wherein a solvent or a mixture of ethylene glycol oligomers is used, the boiling temperature refers to the initial boiling temperature, or the temperature at which any component of the mixture boils.
The dispersant used in the present invention comprises salts of P and X. Wherein P is a polyether functionalized polyacid intermediate formed via the reaction of: (i) a maleic anhydride-containing polymer, (ii) a polyether mono-nucleophile C, and (iii) optionally, a non-polymeric mono-nucleophile D. X is an alkali metal, alkaline earth metal, ammonia, amine or mixtures thereof.
The maleic anhydride-containing polymer has the formula (A) n -(B) m - (E). In the maleic anhydride-containing polymer, a is a maleic anhydride unit having the structure:
b is a styrene or substituted styrene unit having the structure:
wherein R is H or CH 3 Preferably H, R' is halogen, nitro (NO 2 ) A group, or optionally C containing an oxygen atom 1 To C 10 An alkyl group or an aromatic group. The variable e may be 0 to 5, for example 1 to 5, or 0.
E is derived from a monounsaturated monomer containing 2 to 160 carbon atoms or 2 to 45 carbon atoms, which may optionally contain ethers, esters, amides, tertiary amines, acids, halogens, but not alcohols, primary and secondary amines. In one embodiment, E comprises, for example, (meth) acrylic acid repeating units having the structure
Wherein R is H or CH 3 Preferably H, and R 1 Is C optionally comprising two heteroatoms 1 To C 10 Alkyl or aromatic groups, or weight average Molecular Weight (MW) of 150 to 3000 and at C 1 To C 20 Alkyl group-terminated ethylene oxide polyethers and/or propylene oxide polyethers. In another embodiment, E comprises, for example, (meth) acrylamide units having the structure:
wherein R is H or CH 3 ，R 2 And R is 3 Each independently is H or C including a heteroatom 1 To C 20 An alkyl group or an aryl group, or a weight average Molecular Weight (MW) of 150 to 3000 and at C 1 To C 20 Alkyl group-terminated ethylene oxide polyethers and/or propylene oxide polyethers, provided that R 2 And R is 3 Not all are H. In another embodiment, E comprises, for example, (meth) acrylamide repeating units having the structure:
wherein R is H or CH 3 And R is 2 And R is 3 Are joined together to form C 2 To C 16 A cyclic group. In yet another embodiment, E comprises, for example, a vinyl repeat unit having the structure:
wherein R is H or CH 3 And R is 4 Is H or C optionally including heteroatoms such as oxygen or halides 1 To C 20 An alkyl group or an aryl group, or MW is 150 to 3000 and is at C 1 To C 20 Cyclic group-terminated ethylene oxide polyethers and/or propylene oxide polyethers. For clarity, in embodiments in which E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, when an optional polyether group having a MW of 150 to 3000 is included as R 1 、R 2 、R 3 Or R is 4 When these groups have carbon atoms other than 2 to 45 carbon atoms for the monounsaturated monomer of E.
In the maleic anhydride-containing polymer, n is 10 to50, m is 10 to 150, q is 0 to 200, provided that the ratio of n to m is between 1:1 and 1:6. In the polyether-functionalized intermediate P, the units A, B and E can be arranged in a statistical or random structure, or they can have a block structure, where (E) q Forming a block, and (A) n (B) m Together forming another block. The two blocks can be arranged in any combination and are repeated throughout P.
Polyether mono nucleophile C comprises from 6 to 70 ethylene glycol repeat units and optionally comprises propylene glycol repeat units and/or butylene glycol repeat units, provided that at least 50% or at least 70% of all repeat units are ethylene glycol. In one embodiment, C comprises 1 to 15, or even 1 to 10 propylene glycol repeat units. Polyether mono nucleophile C also contains a single alcohol, primary amine or secondary amine group.
The polyether mono nucleophile may be derived from a poly (alkylene oxide) monoalkyl ether monoamine. Exemplary monoamine compounds of this type may be used asAmines or jeffamines TM Amines are commercially available from Huntsman corporation-tion. Specific examples of amines are L-100 (3:19 molar ratio of propylene oxide to ethylene oxide), L-207 (10:33 molar ratio of propylene oxide to ethylene oxide), L-200 (4:41 molar ratio of propylene oxide to ethylene oxide), L-300 (8:58 molar ratio of propylene oxide to ethylene oxide).
When C comprises a single alcohol group, C may be derived from a poly (alkylene oxide) monoalkyl ether. These monoalkyl ethers were purchased from a variety of sources, such as Sigma-Aldrich, croda, BASF, dow and Ineos.
The non-polymeric mono nucleophile D is a linear or branched, saturated or unsaturated alkyl or aryl chain having from 1 to 22 carbon atoms and comprises a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D is substantially free of acid groups or free of acid groups.
In some embodiments in which the non-polymeric mono-nucleophile D comprises a primary amine, the primary amine may comprise methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, dodecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, or mixtures thereof. In some embodiments, the amine may include benzylamine, 2-phenylethylamine (commonly referred to as phenylethylamine), 3-phenylpropylamine, 4-phenylbutylamine, or mixtures thereof. In one embodiment, the primary amine may comprise benzylamine or 2-phenylethylamine. In one embodiment, the primary amine may comprise 2-phenylethylamine.
In some embodiments in which the non-polymeric mono nucleophile D comprises a secondary amine, the secondary amine may be, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N-diisopropylamine, N-diisobutylamine, diisopentylamine, piperidine, N-dimethylpiperidin-4-amine, N-dibenzylamine, N-benzylmethylamine, N-phenyl-N-propylamine, N-methyl-phenethylamine, N-methyl-N- (1-phenethyl) amine, 4-bromo-N-methylbenzylamine, or 4-fluoro-N-methylbenzylamine.
Specific examples of suitable monofunctional nucleophiles D containing hydroxyl functionality include alcohols having an optionally substituted C1-22 alkylene group, such as methanol, ethanol, propan-1-ol, propan-2-ol, butanol, isobutanol, neopentyl alcohol, hexanol, octan-1-ol, 2-ethylhexanol, decanol, dodecanol, oleyl alcohol, stearyl alcohol, behenyl alcohol, cyclohexanol, benzyl alcohol, phenol, octylphenol, nonylphenol, phenylethanol, fluorinated alcohols such as 1H, 2H-perfluoro-1-decanol under the trade name Isofol TM C8-22 branched alcohols (from Sasol).
The maleic anhydride-containing polymer may be prepared by methods known to those skilled in the art and then functionalized with polyether mono-nucleophile C and optionally non-polymeric nucleophile D by any method known in the art. For example, the polyacid may be prepared by esterifying and/or amidating a maleic anhydride-containing copolymer, or the maleic anhydride may be first esterified and/or amidated and then polymerized with styrene and/or substituted styrene using bulk, solution, suspension, or emulsion methods to form the polyacid by any known polymerization technique or combination of polymerization techniques. The polymerization may include free radical, anionic, cationic, atom transfer or group transfer polymerization methods, or combinations thereof.
In the dispersants described herein, one or more maleic anhydride repeat units of a react with polyether nucleophile C and/or non-polymeric nucleophile D to form one or more linkages selected from (i) ester linkages formed from the reaction product of the alcohol groups of polyether nucleophile C and/or non-polymeric nucleophile D with the maleic anhydride repeat units of a; (ii) Salt bonds and/or amide bonds formed by the reaction products of primary or secondary amines of polyether nucleophile C and/or non-polymeric nucleophile D with maleic anhydride repeat units of a; or (iii) an imide bond formed by the reaction product of a primary amine group of a polyether nucleophile C and/or a non-polymeric nucleophile D with a maleic anhydride repeat unit of A.
In another embodiment, the polymer intermediate P may be obtained by reacting a maleic anhydride-containing polymer (number average molecular weight typically between 200 and 50,000 or 700 and 20,000) with a polyether mono-nucleophile C and optionally a non-polymeric nucleophile D, or may be obtained by a reaction of the above, optionally in the presence of a catalyst (such as an acid or base catalyst), optionally with the use of a suitable solvent. In one embodiment of polymer intermediate P, 10% to 100%, or 30% to 100%, or 50% to 100%, or 80% to 100% of the total moles of a are reacted with C; and 0% to 80%, or 0% to 50%, or 0% to 20%, or 0% of the total moles of a is reacted with D; provided that at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90% of a must contain carboxylic acid groups after reaction of the repeating units a with C and D, and that no more than 10%, or 0% to 5% of a units are still able to be in their anhydride form.
The dispersant used in the present invention comprises salts of P and X. X is an alkali metal, alkaline earth metal, ammonia, amine or mixtures thereof.
In some embodiments, salts may be formed by using ammonia, an amine, a quaternary ammonium, or a pyridine cation as X. Examples of amines are methylamine, diethylamine, ethanolamine, diethanolamine, hexylamine, 2-ethylhexylamine, octadecylamine, 2- (dimethylamino) -2-methylpropan-1-ol, 2-dimethylaminoethanol and 2-amino-2-methyl-1-propanol. The quaternary ammonium cation may be a quaternary ammonium cation or a benzalkonium cation. The quaternary ammonium cation may comprise one or two alkyl groups containing from 6 to 20 carbon atoms. Examples of quaternary ammonium cations are tetraethylammonium, N-octadecyl-N, N-trimethylammonium; n, N-didodecyl-N, N-dimethylammonium, N-benzyl-N, N, N-trimethylammonium and N-benzyl-N-octadecyl-N, N-dimethylammonium cations.
In other embodiments, salts may be formed by using an alkali metal or alkaline earth metal as X. For example, monovalent alkali metals (Li, na, K, rb, cs and Fr) or divalent alkaline earth metals (Be, mg, ca, sr, ba and Ra) can be used. In some exemplary embodiments, lithium, sodium, and potassium may be used.
In another embodiment, X may be a polyamine, such as a poly (vinylamine), an alkylene polyamine, or a polyallylamine or a poly (C) 2-6 Alkylene imine), for example, in one embodiment, polyethylene imine. The polyamine or polyalkyleneimine can be linear or branched. The number average molecular weight of the polyamine or polyalkyleneimine can be 140g/mol to 100,000g/mol; more desirably 140 to 75,000; or preferably 200 to 10,000 or 20,000. In some embodiments, X may have a total of at least four primary and/or secondary amine groups per molecule, more desirably at least six primary and/or secondary amine groups.
Examples of polyamines that may be used as X in the present invention may include, but are not limited to: amino-functional polyamino acids such as polylysine from Aldrich Chemical co; amino-functional silicones, which are under the trade nameASi 2122 purchaseFrom Degussa AG; polyamide amine, which is under the trade name +.>Or->Dendrimers were purchased from Aldrich Chemical co; polyallylamines and poly (N-alkyl) allylamines, which are available under the trade name PAA from Nitto Bo-seki; polyvinyl amine, which is available from Mitsubishi Kasei under the trade name +.>Purchased from BASF AG; polyalkyleneimines, such as polyethyleneimine, which are under the trade name +. >Purchased from Nippon Shokubai co., ltd and under the trade name>Purchased from BASF AG; and polytrimethylene imine, which is under the trade namePurchased from DSM AG. The linear polyethyleneimine may be prepared by hydrolysis of poly (N-acyl) alkyleneimines, as described, for example, in Takeo Saegusa et al, macromolecules,1972, volume 5, page 4470. The polytrimethylene imine dendrimer is commercially available from DSM Fine Chemicals and the poly (amidoamine) dendrimer is available from Aldrich Chemical Company as a "Star-burst" dendrimer. The alkylene polyamine can be characterized as having less than 2%, typically less than 1% (by weight) of materials having a boiling point below about 200 ℃ and includes still bottoms, such as ethylene polyamine still bottoms available from Dow Chemical Company (Freeport, texas).
When X is a polyimide, in one exemplary embodiment it is a poly (C 2-6 -alkylene imine) or Polyethyleneimine (PEI). The polyimines may be linear or, in particular, branched.
In one embodiment, X comprises or consists of an amine. In another embodiment, X may comprise a mixture of an amine and an alkali or alkaline earth metal, or a mixture of such metals. In some embodiments where X comprises a mixture of amine and metal, the metal can be present in an amount up to 50 wt%, or in some embodiments, in an amount of no more than 50 wt%, or even no more than 40 wt%, or 30 wt%, or 25 wt%, or 20 wt%, or 10 wt%, or 5 wt%.
Since both P and X may have multiple co-reactive groups, in some cases, there may be more than one bond between them (as defined above). It is also recognized that more than one P may be bonded to a single X. Similarly, there may be more than one X chemically bonded to a single P. However, in one embodiment of the invention, there may be a single P bonded to a single X.
In the dispersants used in the present invention, the polymer intermediate P and the substance X are reacted together such that-CO of P 2 H or-CO 2 - With an amine, metal, or other basic group of X to produce ionic salt and/or covalent bonds, or a mixture of ionic salt and covalent bonds. The weight ratio of P to X is 30:1 to 1:1, or 15:1 to 1:1, or 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, or 2:1.
In one embodiment, the reaction product or copolymer product of P and X may be present as a neat polymer or a polymer in an organic solvent. This can be achieved by dissolving the pure reaction product or copolymer product into a solvent, or by conducting the synthesis of the reaction product or copolymer product in a solvent. In one embodiment, the solvent comprises or consists of: ethylene glycol, ethylene glycol oligomers, or mixtures thereof.
The dispersions used in the present invention also include one or more pigments, or other particulate solid materials. In one embodiment, the solid is an organic pigment, such as any of the well-recognized classes of Pigments described in the third edition of the color Index (1971) and subsequent revisions and supplements thereto, under the section entitled "Pigments". Examples of organic pigments are those from the following: azo, disazo, trisazo, condensed azo, azo lakes, naphthol pigments, anthanthrone, anthrapyrimidine, anthraquinone, benzimidazolone, carbazole, pyrrolopyrroldione, flavanthrone, indigoid pigments, indanthrone, isodibenzanthrone, isoindanthrone, isoindolone, isoindoline, isoanthrone violet, metal complex pigments, oxazine, perylene, viologen, pyranthrone, pyrazoloquinazolinone, quinacridone, quinophthalone, thioindigo, triarylcarbonium pigments, triphenyldioxazine, xanthenes and phthalocyanines, especially copper phthalocyanines and their nuclear halogenated derivatives, and lakes of acid dyes, basic dyes and mordant dyes. Carbon black, while strictly an inorganic pigment, behaves more like an organic pigment in terms of its dispersion properties. In one embodiment, the organic pigment is a phthalocyanine (especially copper phthalocyanine), monoazo, disazo, indanthrone, anthanthrone, quinacridone, pyrrolopyrrole dione, perylene, and carbon black.
Examples of inorganic pigments include metal oxides (such as titanium dioxide, rutile titanium dioxide, and surface-coated titanium dioxide), titanium oxides of different colors (such as yellow and black), iron oxides of different colors (such as yellow, red, brown, and black), zinc oxide, zirconium oxide, aluminum oxide), oxygen-containing metal compounds (such as bismuth vanadate, cobalt aluminate, cobalt stannate, cobalt zincate, zinc chromate, and mixed metal oxides of two or more of manganese, nickel, titanium, chromium, antimony, magnesium, cobalt, iron, or aluminum), prussian blue, vermilion, ultramarine, zinc phosphate, zinc sulfide, molybdates and chromates of calcium and zinc, metallic effect pigments (such as aluminum flakes, copper, and copper/zinc alloys), pearlescent flakes (such as lead carbonate and bismuth oxychloride).
Inorganic solids include extenders and fillers such as ground precipitated calcium carbonate, calcium sulfate, calcium oxide, calcium oxalate, calcium phosphate, calcium phosphonate, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, natural magnesium hydroxide or brucite, precipitated magnesium hydroxide, magnesium carbonate, dolomite, aluminum hydroxide peroxideOr boehmite, calcium and magnesium silicate, aluminosilicates (including nanoclays), kaolinite, montmorillonite (including bentonite, hectorite and saponite), mica, saponite (including muscovite, phlogopite, lepidolite and chlorite), chalk, synthetic precipitated silica, fumed silica, metal fibers and powders, zinc, aluminum, glass fibers, refractory fibers, carbon black (including single-walled and multi-walled carbon nanotubes, enhanced carbon black and non-enhanced carbon black), graphite, buckyballs, asphaltenes, graphene, diamond, alumina, quartz, silica gel, wood flour, wood chips (including cork and hardwood), saw dust, powdered paper/fiber, cellulosic fibers (such as kenaf, hemp, sisal, flax, cotton linters, jute, ramie, rice hulls or chaff, raffinum, typha reeds, coconut fibers, coconut shell fibers, oil palm fibers, kapok, banana leaves, carob, fenugreek, agave fiber leaves, flax leaves, abaca, bagasse, straw, bamboo strips, wheat flour, MDF, etc.), vermiculite, zeolite, hydrotalcite, fly ash from power plants, incineration sewage sludge ash, pozzolans, blast furnace slag, asbestos, temperature asbestos, direct rock, blue rock, wollastonite, attapulgite, etc., particulate ceramic materials (such as alumina, zirconia, titania, ceria, silicon nitride, aluminum nitride, boron carbide, mixed metal-aluminum nitride, and aluminum nitride salts); particulate magnetic materials, such as magnetic oxides of transition metals (typically iron and chromium), e.g. gamma-Fe 2 O 3 、Fe 3 O 4 And cobalt doped iron oxides, ferrites (such as barium ferrites); and metal particles such as metallic aluminum, iron, nickel, cobalt, copper, silver, gold, palladium, and platinum, and alloys thereof.
Other useful solid materials include flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine cyanurate, antimony oxide, and borates.
In a specific embodiment of the invention, the pigment comprises or consists of carbon black.
The dispersions of the present invention may be prepared by methods known and understood by those skilled in the art. In some embodiments, the dispersion used in the methods of the present invention comprises 0.5 to 40 wt% pigment, 0.5 to 40 wt% dispersant described herein, and 20 to 99 wt% solvent. As described herein and understood by those skilled in the art, small amounts of other additives may be included in the dispersion. In one embodiment, the solvent is primarily or exclusively ethylene glycol. In another embodiment, the solvent is predominantly or exclusively ethylene glycol oligomer having from 2 to 5 ethylene glycol repeat units.
In one embodiment, the dispersant used in the method of the present invention has a pH of greater than or equal to 5, or even greater than or equal to 7, when measured in a 50% ethylene glycol solution of the dispersant.
After preparing the dispersion comprising the solvent, the dispersant and the pigment (all as described above), the method of the present invention further comprises the step of adding to the dispersion a material having a boiling point higher than the temperature (T), wherein the temperature (T) is the boiling point of the solvent. In one embodiment, the solvent comprises or consists of ethylene glycol or an ethylene glycol oligomer having 2 to 5 repeating units. In such embodiments, the temperature T may be at least 180 ℃, or 190 ℃, or 195 ℃, or even at least 200 ℃. Substances having a boiling point above temperature T may include other solvents, but may also include reactive monomer components. In a specific embodiment, the material having a boiling point above temperature (T) comprises monomers formed from the reaction product of a lower aliphatic diol with dimethyl terephthalate or the reaction product of a lower aliphatic diol with terephthalic acid. Substances having a boiling point above temperature (T) may also include bis (2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or mixtures thereof.
After or while mixing the substance having a boiling temperature above (T) with the dispersion described herein, the mixture is heated to a temperature of at least T or higher. In some embodiments, the mixture is heated to a temperature above 180 ℃, or 190 ℃, or 195 ℃, or 200 ℃, or even at least 250 ℃ (e.g., 200 ℃ to 300 ℃, or even 250 ℃ to 295 ℃). The dispersants of the present invention unexpectedly provide pigment dispersions that are stable at elevated temperatures.
In one embodiment, the colored polymer produced by the process of the present invention is polyethylene terephthalate (PET). Methods of making PET are known to those skilled in the art and are described in references such as U.S. patent publication No. 2003/0105214, which is incorporated herein by reference. In this process, the monomers used to prepare the PET polymer are formed by transesterification or esterification reactions. These monomers are prepared by transesterification or esterification of dimethyl terephthalate with a lower aliphatic diol such as ethylene glycol or monoethylene glycol or terephthalic acid with a lower aliphatic diol such as ethylene glycol or monoethylene glycol. The product of the transesterification or esterification reaction includes bis (2-hydroxyethyl) terephthalate or 2-hydroxyethyl terephthalic acid. In one embodiment of the invention, the dispersion described herein and the product of the transesterification or esterification reaction are mixed and then heated to a temperature of at least 180 ℃, or at least 190 ℃, or at least 195 ℃, or at least 200 ℃, or even at least 250 ℃ (e.g., 200 ℃ to 300 ℃), or even 250 ℃ to 295 ℃.
In one embodiment, the polymer prepared by the process of the present invention comprises from 0.01% to 20% by weight of pigment based on the weight of the polymer, further for example from 0.1% to 2% by weight, or even from 0.4% to 1.6% by weight. In one exemplary embodiment, the pigment comprises carbon black.
The following examples provide an illustration of the invention. These examples are not exhaustive and are not intended to limit the scope of the invention.
Examples
A series of polymer intermediates (Z) were prepared as follows:
intermediate 1: poly (styrene-co-maleic anhydride) (Xiran 2000P, polyscope) (50.00 parts) and ethyl acetate (240.06 parts) were heated at 50℃for 0.5 hours. Polyetheramine (Surfonamine L-207) (310.09 parts) was charged into a reaction vessel and heated at 70℃for 4 hours. The reaction was fitted with a solvent trap and heated at 80℃for 11.25 hours. The reaction was heated at 90 ℃ for 6.5 hours to give a clear yellow liquid. Acid value= 24.98mg KOH g-1, amine value=1.66 mg KOH g-1, active content=100.00%.
Intermediate 2: poly (styrene-co-maleic anhydride) (Xiran 2000P, polyscope) (8.00 parts) and ethyl acetate (54.95 parts) were heated at 50℃for 1 hour. Polyetheramine (Surfonamine L-300) (74.42 parts) was charged into a reaction vessel and heated at 70℃for 3.5 hours. The reaction was fitted with a solvent trap and heated at 80 ℃ for 4 hours. The reaction was heated at 90 ℃ for 4.33 hours to give an opaque yellow solid. Acid number=21.95 mg KOH g-1, amine number=2.21 mg KOH g-1, active content=100.00%.
Intermediate 3: poly (styrene-co-maleic anhydride) (Xiran 2000P, polyscope) (12.51 parts) and propylene glycol monomethyl ether acetate (58.09 parts) were heated at 70℃for 1 hour. Polyetheramine (Surfonamine L-207) (42.30 parts) was charged to the reaction vessel and heated at 110℃for 0.66 hours over 0.5 hours. 3- (dimethylamino) -1-propylamine (2.08 parts) was charged into the reaction vessel and heated at 130℃for 2 hours. The reaction was fitted with a solvent trap and heated at 170 ℃ for 30 hours to give a clear yellow viscous liquid. Acid number=8.19 mg KOH g-1, amine number=20.63 mg KOH g-1, active content=100.00%.
Intermediate 4: poly (styrene-co-maleic anhydride) (Xiran 2000P, polyscope) (12.51 parts) and ethyl acetate (52.13 parts) were heated at 50℃for 1 hour. Polyetheramine (Surfonamine L-207) (16.89 parts) was charged into a reaction vessel and heated at 50℃for 3 hours. Polyethylene glycol monomethyl ether MW1000 (20.41 parts) is charged to a reaction vessel and heated at 70℃for 19.5 hours. Phenethylamine (1.24 parts) was charged into the reaction vessel and heated at 70℃for 23 hours. The reaction was fitted with a solvent trap and heated at 85 ℃ for 4.5 hours to give an opaque amber solid. Acid number=38.77 mg KOH g-1, amine number=0 mg KOH g-1, active content=100.00%.
Intermediate 5: poly (styrene-co-maleic anhydride) (Xiran EF60, polyscope) (22.00 parts) and ethyl acetate (53.21 parts) were heated at 50℃for 20 minutes. Polyetheramine (Surfonamine L-207) (57.82 parts) was charged into a reaction vessel and heated at 70℃for 4 hours. The reaction was fitted with a solvent trap and heated at 90 ℃ for 13 hours to give a clear brown viscous liquid. Acid number=21.99 mg KOH g-1, amine number=0 mg KOH g-1, active content=100.00%.
Intermediate 6: poly (styrene-co-maleic anhydride) (Xiran 1000P, polyscope) (13.00 parts) and ethyl acetate (54.22 parts) were heated at 50℃for 40 minutes. Polyetheramine (Surfonamine L-207) (64.29 parts) was charged into a reaction vessel and heated at 70℃for 3 hours. Phenethylamine (1.75 parts) and 1-decanol (2.29 parts) were charged into a reaction vessel and heated at 70℃for 14.75 hours. The reaction was fitted with a solvent trap and heated at 90 ℃ for 9.25 hours to give a clear brown liquid. Acid number=37.11 mg KOH g-1, amine number=2.00 mg KOH g-1, active content=100.00%.
A series of dispersant examples were prepared or provided as follows. The pH of the dispersant was measured using a 50% dispersant in ethylene glycol:
example 1: intermediate 1 (25.00 parts) and ethylene glycol (27.50 parts) were heated at 60 ℃. 2-dimethylamino-2-methylpropanol (80% aqueous solution) (2.50 parts) was added to the resultant material and heated for 0.25 hours to obtain a clear pale yellow solution. Active content = 45.5%, pH = 9.
Example 2: intermediate 1 (25.00 parts) and ethylene glycol (30.00 parts) were heated at 60 ℃. 2-dimethylamino-2-methylpropanol (80% aqueous solution) (5.00 parts) was added to the resultant material and heated for 0.25 hours to obtain a clear pale yellow solution. Active content = 40.9%, pH = 9.
Example 3: intermediate 2 (40.00 parts) and ethylene glycol (44.00 parts) were heated at 60 ℃. 2-dimethylamino-2-methylpropanol (80% aqueous solution) (4.00 parts) was added to the resultant material and heated for 0.5 hours to obtain a clear pale yellow solution. Active content = 45.5%, pH = 9.
Example 4: intermediate 3 (1.05 parts) and ethylene glycol (7.45 parts) were heated at 70 ℃. 2-dimethylamino-2-methylpropanol (80% aqueous solution) (0.21 part) was added to the resultant material and heated for 0.5 hours to obtain a clear pale yellow solution. Active content = 11.97%, pH = 9.
Example 5: intermediate 4 (1.05 parts) and ethylene glycol (7.45 parts) were heated at 70 ℃. 2-dimethylamino-2-methylpropanol (80% aqueous solution) (0.21 part) was added to the resultant material and heated for 0.5 hours to obtain a clear pale yellow solution. Active content = 11.73%, pH = 9.
Example 6: intermediate 1 (15.15 parts) and ethylene glycol (16.57 parts) were heated at 50 ℃. 2-amino-2-methyl-1-propanol (95% aqueous solution) (1.52 parts) was added to the resultant mass, and heated for 0.50 hours to give a clear colorless solution. Active content = 46.11%, pH = 9.
Example 7: intermediate 5 (18.62 parts) and ethylene glycol (20.48 parts) were heated at 60 ℃. 2- (dimethylamino) -ethanol (1.86 parts) was added to the resulting material and heated for 0.25 hours to give a clear amber solution. Active content = 44.95%, pH = 8.
Example 8: intermediate 6 (20.22 parts) and ethylene glycol (22.24 parts) were heated at 50 ℃. 2- (dimethylamino) -ethanol (2.02 parts) was added to the resulting material and heated for 0.33 hours to give a clear brown solution. Active content = 44.44%, pH = 8.
Example 9: intermediate 1 (33.81 parts) and ethylene glycol (37.19 parts) were heated at 50 ℃. Triethylamine (3.38 parts) was added to the resulting material and heated for 0.25 hours to give a clear yellow solution. Active content = 45.80%, pH = 9.
Comparative example 1: orotan SN (Dow) -naphthalene sulfonic acid-formaldehyde condensate.
Comparative example 2: morwet D-809 (Nouryon) -naphthalene sulfonic acid-formaldehyde condensate
Comparative example 3: intermediate 6
Test 1-high temperature test 200 ℃ C: 1.05g of the example or comparative example to be tested (100% active material excluding ethylene glycol or water, i.e., 2.10g of 50% active material would be used) and 7.45g of ethylene glycol (which value is reduced by the amount of inactive material added as part of the example or comparative example, i.e., 6.40g for 50% active material) were filled into 32mL vials and shaken until the sample was completely dissolved. Glass beads (17.00 g) and carbon Black (specialty Black 4,1.50 g) were filled into vials and the vials were sealed. The material was then placed on a horizontal shaker for 16 hours to produce a millbase. The millbase (1.00 g) was removed from the vial and filled into 32mL vials. Ethylene glycol (6.75 g) was charged to the vial and the contents stirred until uniform to produce a diluted millbase. The vials were heated to 200 ℃. Once the diluted millbase reaches 200 ℃, it is checked to determine if it is homogeneous. Heterogeneous materials have a much larger proportion of pigment at the bottom of the vial, whereas homogeneous materials are acceptable. The results are summarized in table 1.
TABLE 1
Examples Results
Comparative example 1 Homogenizing
Comparative example 2 Homogenizing
Comparative example 3 Homogenizing
1 Homogenizing
2 Homogenizing
3 Homogenizing
4 Homogenizing
5 Homogenizing
6 Homogenizing
7 Homogenizing
8 Homogenizing
9 Homogenizing
Test 2: a material having a boiling point higher than that of the ethylene glycol solvent (bis (2-hydroxyethyl) terephthalate ("BHET")): the material from run 1 was transferred to run 2. BHET (7.75 g) was filled into vials at 200deg.C. Once the BHET melted, the sample was stirred and heated for an additional 1 hour. This procedure was repeated two more times so that a total of 23.25g BHET was added and the sample was heated for a total of 3 hours. The sample was allowed to cool to room temperature. Once the sample has cooled, it is first checked to determine homogeneity, where the heterogeneous sample has either a black spot everywhere, a layer of black material at the bottom, or both. Next, the color is determined. The quality is a homogeneous sample with a black color. The results are summarized in table 2.
TABLE 2
Examples Homogeneity of Color of
Comparative example 1 Heterogeneous material Gray color
Comparative example 2 Heterogeneous material Gray color
Comparative example 3 Homogenizing Gray color
1 Homogenizing Black color
2 Homogenizing Black color
3 Homogenizing Black color
4 Homogenizing Black color
5 Homogenizing Black color
6 Homogenizing Black color
7 Homogenizing Black color
8 Homogenizing Black color
9 Homogenizing Black color
This test shows that the pigment dispersions described herein can be used at elevated temperatures (e.g., the temperature required to polymerize PET polymers).
Each of the documents mentioned above is incorporated by reference herein, including any prior application requiring priority thereto, whether or not specifically listed above. The mention of any document is not an admission that the document is entitled to prior art or constitutes a general knowledge of any jurisdiction technician. Unless explicitly indicated otherwise or in the examples, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc. are to be understood as modified by the word "about". It is to be understood that the upper and lower limits of the amounts, ranges and proportions described herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used with ranges or amounts for any other element.
As used herein, the transitional term "comprising" synonymous with "comprising," "containing," or "characterized by" is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each recitation of "comprising" herein, the term is intended to be an alternative, narrower embodiment, also covering the phrases "consisting essentially of … …" and "consisting of … …," wherein "consisting of … …" excludes any elements or steps not indicated, and "consisting essentially of … …" allows for the inclusion of additional, unrecited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.
While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this regard, the scope of the invention is limited only by the following claims.

Claims (27)

1. A method of forming a pigment dispersion stable at elevated temperatures, comprising:
(1) Preparing a dispersion comprising
(a) A solvent, wherein the solvent has a boiling temperature (T) and wherein the solvent comprises or consists of ethylene glycol or an ethylene glycol oligomer;
(b) A pigment; and
(c) A dispersant comprising a salt of P and X; wherein P is a polyether functionalized polyacid intermediate formed via the reaction of: (i) a maleic anhydride-containing polymer, (ii) a polyether mono-nucleophile C, and (iii) optionally, a non-polymeric mono-nucleophile D, and X is an alkali metal, alkaline earth metal, ammonia, amine, or mixtures thereof;
(i) Wherein the maleic anhydride-containing polymer has the formula (A) n -(B) m -(E) q ；
Wherein a is a maleic anhydride unit having the structure:
b is a styrene or substituted styrene unit having the structure:
Wherein R is H or CH 3 R' is a halogen, a nitro group, or C optionally containing an oxygen atom 1 To C 10 An alkyl group or an aromatic group, and e is 0 to 5;
e is derived from a monounsaturated monomer containing from 2 to 160 or from 2 to 45 carbon atoms, which may optionally contain ethers, esters, amides, tertiary amines,
Acids, halogens, but not alcohols, primary and secondary amines;
wherein n is 10 to 50, m is 10 to 150, q is 0 to 200, provided that the ratio of n to m is between 1:1 and 1:6;
(ii) Wherein the polyether mono-nucleophile C comprises 6 to 70 ethylene glycol repeat units and optionally comprises propylene glycol repeat units and/or butylene glycol repeat units, provided that at least 50% or at least 70% of all repeat units are ethylene glycol, and wherein the polyether mono-nucleophile C comprises a single alcohol, primary amine, or secondary amine group;
(iii) Wherein the non-polymeric mono nucleophile D is a linear or branched, saturated or unsaturated alkyl or aryl chain having from 1 to 22 carbon atoms and comprises a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D is substantially free of acid groups or free of acid groups;
wherein 10% to 100%, or 30% to 100%, of the total mole number of A,
Or 50% to 100%, or 70% to 100% with C; and 0% to 80%, or 0% to 50%, or 0% to 25% of the total moles of a is reacted with D; provided that after the reaction of the repeating units A with C and D,
at least 20%, or at least 30%, or at least 40%, or at least 50% >,
or at least 60%, or at least 70%, or at least 80%, or at least 90% of a must contain carboxylic acid groups and no more than 10%, or 0% to 5% of a units can still be in their anhydride form;
(2) Adding a substance having a boiling point higher than the temperature (T); and
(3) The dispersion is heated at least to the boiling temperature (T) of the solvent.
2. The method of claim 1, wherein the weight ratio of P to X is 30:1 to 1:1, or 15:1 to 1:1.
3. The method of claim 1 or 2, wherein E comprises a (meth) acrylic acid repeating unit having the structure:
wherein R is H or CH 3 And R is 1 Is C comprising two hetero atoms 1 To C 10 Alkyl or aromatic groups, or weight average Molecular Weight (MW) of 150 to 3000 and at C 1 To C 20 Alkyl group-terminated ethylene oxide polyethers and/or propylene oxide polyethers.
4. A method according to any one of claims 1 to 3, wherein E comprises a (meth) acrylamide repeating unit having the structure:
Wherein R is H or CH 3 ，R 2 And R is 3 Each independently is H or C including a heteroatom 1 To C 20 An alkyl group or an aryl group, or a weight average Molecular Weight (MW) of 150 to 3000 and at C 1 To C 20 Alkyl group-terminated ethylene oxide polyethers and/or propylene oxide polyethers, provided that R 2 And R is 3 Not all are H.
5. The method of any one of claims 1 to 4, wherein E comprises a (meth) acrylamide repeating unit having the structure:
wherein R is H or CH 3 ，R 2 And R is 3 Are joined together to form C 2 To C 16 A cyclic group.
6. The method of any one of claims 1 to 5, wherein E comprises a vinyl repeat unit having the structure:
wherein R is H or CH 3 And R is 4 Is H or C optionally including heteroatoms such as oxygen or halides 1 To C 20 An alkyl group or an aryl group, or MW is 150 to 3000 and is at C 1 To C 20 Cyclic group-terminated ethylene oxide polyethers and/or propylene oxide polyethers.
7. The method of any one of claims 3 to 6, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R 1 、R 2 、R 3 Or R is 4 Including MW of 150 to 3000 and at C 1 To C 20 A cyclic group-terminated ethylene oxide polyether and/or propylene oxide polyether or consists of the ethylene oxide polyether and/or propylene oxide polyether, wherein the carbon atoms in the polyether are carbon atoms other than n carbon atoms in the monounsaturated monomer.
8. The method of any one of claims 1 to 7, wherein C comprises 1 to 15 or 1 to 10 propylene glycol repeat units.
9. The method of any one of claims 1 to 8, wherein X is an amine.
10. The method according to any one of claims 1 to 8, wherein X comprises a mixture of an amine and an alkali metal and/or alkaline earth metal, and wherein the alkali metal and/or alkaline earth metal comprises no more than 50% or 40% or 30% or 20% or 10% by weight of X.
11. The method of any one of claims 1 to 10, wherein the pigment comprises or consists of carbon black.
12. The method of any one of claims 1 to 11, wherein the solvent comprises or consists of ethylene glycol.
13. The method of any one of claims 1 to 12, wherein the solvent comprises or consists of a glycol oligomer having 2 to 5 glycol repeat units.
14. The method of any one of claims 1 to 13, wherein the dispersion comprises 0.5 to 40 wt% pigment, 0.5 to 40 wt% dispersant, and 20 to 99 wt% solvent.
15. The process according to any one of claims 1 to 14, wherein the substance having a boiling point higher than temperature (T) is selected from bis (2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or mixtures thereof.
16. The method according to any one of claims 1 to 15, wherein the temperature (T) is at least 180 ℃, or at least 190 ℃, or at least 195 ℃, or at least 200 ℃, or 200 ℃ to 300 ℃, or 250 ℃ to 295 ℃.
17. Use of a dispersant to provide a stable pigment dispersion at a temperature of at least 180 ℃, or at least 190 ℃, or at least 195 ℃ or at least 200 ℃, wherein the dispersant comprises:
salts of P and X; wherein P is a polyether functionalized polyacid intermediate formed via the reaction of: (i) a maleic anhydride-containing polymer, (ii) a polyether mono-nucleophile C, and (iii) optionally, a non-polymeric mono-nucleophile D, and X is an alkali metal, alkaline earth metal, ammonia, amine, or mixtures thereof;
(i) Wherein the maleic anhydride-containing polymer has the formula (A) n -(B) m -(E) q ；
Wherein a is a maleic anhydride unit having the structure:
b is a styrene or substituted styrene unit having the structure:
wherein R is H or CH 3 R' is a halogen, a nitro group, or C optionally containing an oxygen atom 1 To C 10 An alkyl group or an aromatic group, and e is 0 to 5; ,
e is derived from a monounsaturated monomer containing 1 to 160 or 2 to 45 carbon atoms,
it may optionally contain ethers, esters, amides, tertiary amines, acids, halogens, but not alcohols, primary and secondary amines;
wherein n is 10 to 50, m is 10 to 150, q is 0 to 200, provided that the ratio of n to m is between 1:1 and 1:6;
(ii) Wherein the polyether mono-nucleophile C comprises 6 to 70 ethylene glycol repeat units and optionally comprises propylene glycol repeat units and/or butylene glycol repeat units, provided that at least 50% or at least 70% of all repeat units are ethylene glycol, and wherein the polyether mono-nucleophile C comprises a single alcohol, primary amine, or secondary amine group;
(iii) Wherein the non-polymeric mono nucleophile D is a linear or branched, saturated or unsaturated alkyl or aryl chain having from 1 to 22 carbon atoms and comprises a single alcohol, primary or secondary amine group, and optionally one or more tertiary amine, halide or nitro groups, provided that D is substantially free of acid groups or free of acid groups;
wherein 10% to 100%, or 30% to 100%, or 50% to 100%, or 70% to 100% of the total moles of a are reacted with C; and 0% to 80%, or 0% to 50%, or 0% to 25% of the total moles of a is reacted with D; provided that at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90% of a must contain carboxylic acid groups after reaction of the repeating units a with C and D, and that no more than 10%, or 0% to 5% of a units are still able to be in their anhydride form.
18. Use of a dispersant as claimed in claim 17 wherein the dispersion comprises:
a solvent, wherein the solvent comprises or consists of ethylene glycol or an ethylene glycol oligomer, and a pigment, wherein the pigment comprises or consists of carbon black.
19. Use of a dispersant as claimed in claim 17 or 18 wherein the weight ratio of P to X is from 30:1 to 1:1, or from 15:1 to 1:1.
20. Use of a dispersant as claimed in claims 17 to 19 wherein E comprises a (meth) acrylic acid repeat unit having the structure:
wherein R is H or CH 3 And R is 1 Is C comprising two hetero atoms 1 To C 10 Alkyl or aromatic groups, or weight averageMolecular Weight (MW) is 150 to 3000 and is C 1 To C 20 Alkyl group-terminated ethylene oxide polyethers and/or propylene oxide polyethers.
21. Use of a dispersant as claimed in claims 17 to 20 wherein E comprises a (meth) acrylamide repeating unit having the structure:
wherein R is H or CH 3 ，R 2 And R is 3 Each independently is H or C including a heteroatom 1 To C 20 An alkyl group or an aryl group, or a weight average Molecular Weight (MW) of 150 to 3000 and at C 1 To C 20 Alkyl group-terminated ethylene oxide polyethers and/or propylene oxide polyethers, provided that R 2 And R is 3 Not all are H.
22. Use of a dispersant as claimed in claims 17 to 21 wherein E comprises a (meth) acrylamide repeating unit having the structure:
wherein R is H or CH 3 ，R 2 And R is 3 Are joined together to form C 2 To C 16 A cyclic group.
23. Use of a dispersant as claimed in claims 17 to 22 wherein E comprises a vinyl repeat unit having the structure:
wherein R is H or CH 3 And R is 4 Is H or optionally includesC being hetero atoms, e.g. oxygen or halides 1 To C 20 An alkyl group or an aryl group, or MW is 150 to 3000 and is at C 1 To C 20 Cyclic group-terminated ethylene oxide polyethers and/or propylene oxide polyethers.
24. Use of a dispersant as claimed in any one of claims 3 to 6 wherein E is derived from a monounsaturated monomer having from 2 to 45 carbon atoms, and wherein R 1 、R 2 、R 3 Or R is 4 Including MW of 150 to 3000 and at C 1 To C 20 A cyclic group-terminated ethylene oxide polyether and/or propylene oxide polyether or consists of the ethylene oxide polyether and/or propylene oxide polyether, wherein the carbon atoms in the polyether are carbon atoms other than the n carbon atoms in the monounsaturated monomer.
25. Use of a dispersant as claimed in claims 17 to 24 wherein C comprises from 1 to 15 or from 1 to 10 propylene glycol repeat units.
26. Use of a dispersant as claimed in claims 17 to 25 wherein X is an amine.
27. Use of a dispersant as claimed in any one of claims 17 to 25 wherein X comprises a mixture of an amine and an alkali metal and/or alkaline earth metal and wherein the alkali metal and/or alkaline earth metal comprises no more than 50% or 40% or 30% or 20% or 10% by weight of X.
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