Process for preparing a polymer using a pigment dispersion

Abstract

The invention provides a method for preparing a polymer using a pigment dispersion stable at elevated temperatures, wherein the dispersion comprises a pigment, a solvent and a dispersant, which is a salt of a polyether-functionalized polyacid.

Description

Technical Field

[0001] The disclosed technology relates to a method for preparing colored polymers using pigment dispersions that are stable at elevated temperatures. Summary of the Invention

[0002] The present invention relates to a method for preparing a polymer using a pigment dispersion that is stable at elevated temperatures, the method comprising the steps of: (1) providing a pigment dispersion comprising (a) a solvent having a boiling temperature (T), wherein the solvent comprises or is composed of ethylene glycol or ethylene glycol oligomers, (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 to at least the boiling temperature (T) of the solvent.

[0003] The dispersant used in this invention comprises a salt of P and X. P is a polyether-functionalized polyacid intermediate formed by the reaction of the following substances: (i) a polymer containing maleic anhydride, (ii) a polyether monophilic nucleophilic reagent C, and (iii) optionally, a nonpolymeric monophilic nucleophilic reagent D. X may be an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof.

[0004] In the dispersants used in the methods described herein, the polymers containing maleic anhydride have formula (A). n -(B) m -(E) q Wherein, A is a maleic anhydride unit having the following structure:

[0005]

[0006] B is a styrene or substituted styrene unit having the following structure:

[0007]

[0008] Wherein R is H or CH3, preferably H, and R′ is a halogen, a nitro (NO2) group, or optionally a C1 to C2 group containing an oxygen atom. 10 The alkyl or aromatic group, e is 0 to 5, for example 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 excludes alcohols, primary amines, and secondary amines. In polymers containing maleic anhydride, n is 10 to 50, m is 10 to 150, and q is 0 to 200, preferably 0, provided that the ratio of n to m is between 1:1 and 1:6.

[0009] The polyether monophilic nucleophile C comprises 6 to 70 ethylene glycol repeating units, and optionally propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% or at least 70% of all repeating units are ethylene glycol. The polyether monophilic nucleophile C comprises a single alcohol, primary amine, or secondary amine group. The non-polymeric monophilic nucleophile D is a straight-chain or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms, and comprises a single alcohol, primary amine, 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 contains no acid groups.

[0010] In the polyether-functionalized polybasic acid P, 10% to 100%, or 30% to 100%, or 50% to 100%, or 70% to 100% of the total molar number of A reacts with C; and 0% to 80%, or 0% to 50%, or 0% to 25% of the total molar number of A reacts with D; provided that after the repeating unit A reacts 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 10%, or 0% to 5% of A units can still be in their anhydride form;

[0011] The present invention also includes the use of the above-mentioned dispersant to provide stable pigment dispersions at elevated temperatures. Detailed Implementation

[0012] Definitions. To simplify this disclosure, we will use parentheses around "methyl" to indicate that the named molecule may optionally include a methyl substituent, such as (meth)acrylic acid will refer to methacrylic acid and / or acrylic acid, and methyl (meth)acrylate will refer to methacrylate and / or acrylate. We intend that the polyethers used herein may be random polyethers or block polyethers, and we do not intend that they limit the polyether to a single block or multiple blocks of any particular repeating unit. We will use the symbol C(=O)-OH to represent any form of carboxylic acid, such as the acid form, salt form, or, if two carboxylic acids are physically adjacent and capable of forming an anhydride ring, the anhydride form. If C(=O)-OH is adjacent to the nitrogen of an amide bond, we also expect it to be capable of converting to C(=O)- as part of an imide. We will use the term "hydrocarbon group" to describe a hydrocarbon group with one hydrogen atom removed. A hydrocarbon group in this specification will mean a hydrocarbon-like group, and for every four carbon atoms in the group, it may include at most one oxygen or nitrogen atom, but preferably only carbon and hydrogen atoms. An alkylene group will mean a hydrocarbon with two hydrogen atoms removed. For every two carbon atoms in the group, the alkylene group will optionally also include at most one oxygen or nitrogen atom, but preferably only carbon and hydrogen atoms. To avoid ambiguity, when counting carboxylic acid groups or carbonyl groups, we count the anhydrides of dicarboxylic acids and imides as two carbonyl groups.

[0013] This invention relates to a method for 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 is composed of ethylene glycol or ethylene glycol oligomers, (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 equal to the boiling temperature (T) of the solvent. The invention also includes the use of the dispersant to provide a stable pigment dispersion at elevated temperatures.

[0014] The solvents used in this invention comprise ethylene glycol or ethylene glycol oligomers, or mixtures thereof. In one embodiment, the solvent comprises or is composed of ethylene glycol. In another embodiment, the solvent comprises or is composed of ethylene glycol oligomers. When the solvent comprises or is composed of ethylene glycol oligomers, these oligomers may contain 2 to 5 repeating ethylene glycol units. If the dispersion used in this invention comprises one or more other co-solvents, these solvents may be selected from water, alkanols, alkanocarboxylic 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°C, or at least 190°C, or at least 195°C, or at least 200°C. For example, ethylene glycol has a boiling temperature of 197°C. In embodiments in which a mixture of solvent or 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.

[0015] The dispersant used in this invention comprises a salt of P and X. P is a polyether-functionalized polyacid intermediate formed via a reaction of: (i) a polymer containing maleic anhydride, (ii) a polyether monophilic nucleophilic reagent C, and (iii) optionally, a non-polymeric monophilic nucleophilic reagent D. X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof.

[0016] Polymers containing maleic anhydride have formula (A). n -(B) m -(E). In polymers containing maleic anhydride, A is a maleic anhydride unit having the following structure:

[0017]

[0018] B is a styrene or substituted styrene unit having the following structure:

[0019]

[0020] Wherein R is H or CH3, preferably H, and R′ is a halogen, a nitro (NO2) group, or optionally a C1 to C2 group containing an oxygen atom. 10 Alkyl or aromatic groups. The variable e can be 0 to 5, for example 1 to 5, or 0.

[0021] 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, or halogens, but excludes alcohols, primary amines, and secondary amines. In one embodiment, E comprises, for example, a repeating (meth)acrylic acid unit having the following structure:

[0022]

[0023] Wherein R is H or CH3, preferably H, and R1 is C1 to C1, which optionally contains two heteroatoms. 10 Alkyl or aromatic groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers. In another embodiment, E comprises, for example, a (meth)acrylamide unit having the following structure:

[0024]

[0025] Where R is H or CH3, and R2 and R3 are each independently H or C1 to C containing heteroatoms. 20 Alkyl or aryl groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers, provided that R2 and R3 cannot both be H. In another embodiment, E comprises, for example, a (meth)acrylamide repeating unit having the following structure:

[0026]

[0027] Where R is H or CH3, and R2 and R3 are connected together to form C2 to C3. 16 Cyclic groups. In yet another embodiment, E comprises, for example, a vinyl repeating unit having the following structure:

[0028]

[0029] Where R is H or CH3, and R4 is H or optionally contains heteroatoms such as oxygen or halides C1 to C2. 20 Alkyl or aryl groups, or MW is 150 to 3000 and is C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers. For clarity, in embodiments where E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, when optional polyether groups comprising MW of 150 to 3000 are used as R1, R2, R3, or R4, the carbon atoms of these groups are carbon atoms other than the 2 to 45 carbon atoms of the monounsaturated monomer used for E.

[0030] In polymers containing maleic anhydride, n is 10 to 50, m is 10 to 150, and 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, units A, B, and E can be arranged in a statistical or random structure, or they can have a block structure, wherein (E) q This forms a segment, and (A) n(B) m The two segments can be combined to form another segment. These two segments can be arranged in any combination and can be repeated throughout P.

[0031] The polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally includes propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% or at least 70% of all repeating units are ethylene glycol. In one embodiment, C comprises 1 to 15, or even 1 to 10 propylene glycol repeating units. The polyether monophilic nucleophilic reagent C also comprises a single alcohol, primary amine, or secondary amine group.

[0032] Polyether mononuclear reagents can be derived from poly(epoxide) monoalkyl ether monoamines. Exemplary monoamine compounds of this type can be used as… amine or Jeffamine TM The amine was purchased commercially from Huntsman Corporation. Specific examples of amines are L-100 (molar ratio of propylene oxide to ethylene oxide is 3:19), L-207 (molar ratio of propylene oxide to ethylene oxide is 10:33), L-200 (molar ratio of propylene oxide to ethylene oxide is 4:41), and L-300 (molar ratio of propylene oxide to ethylene oxide is 8:58).

[0033] When C contains a single alcohol group, C can be derived from poly(epoxy) monoalkyl ethers. These monoalkyl ethers are available from a variety of sources, such as Sigma-Aldrich, Croda, BASF, Dow, and Ineos.

[0034] The nonpolymeric monophilic nucleophilic reagent D is a straight or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms and containing 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 contains no acid groups.

[0035] In some embodiments where the nonpolymerized monophilic nucleophilic reagent D comprises a primary amine, the primary amine may include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine, nonadecanamine, eicosamine, 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 include benzylamine or 2-phenylethylamine. In one embodiment, the primary amine may include 2-phenylethylamine.

[0036] In some embodiments where the nonpolymerized monophilic nucleophilic reagent D comprises a secondary amine, the secondary amine may be, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N,N-diisopropylamine, N,N-diisobutylamine, diisopentylamine, piperidine, N,N-dimethylpiperidin-4-amine, N,N-dibenzylamine, N-benzylmethylamine, N-phenyl-N-propylamine, N-methyl-Phenethylamine, N-methyl-N-(1-phenylethyl)amine, 4-bromo-N-methylbenzylamine, or 4-fluoro-N-methylbenzylamine.

[0037] Specific examples of suitable monofunctional nucleophiles D containing a hydroxyl functional group include alcohols having optionally substituted C1-22 alkylene groups, such as methanol, ethanol, propan-1-ol, propan-2-ol, butanol, isobutanol, neopentyl alcohol, hexanol, octyl-1-ol, 2-ethylhexanol, decanol, dodecyl alcohol, oleyl alcohol, stearyl alcohol, dodecyl alcohol, cyclohexanol, benzyl alcohol, phenol, octylphenol, nonylphenol, phenylethanol, fluorinated alcohols such as 1H,1H,2H,2H-perfluoro-1-decyl alcohol, and those marketed under the trademark Isofol. TM C8-22 branched alcohol (obtained from Sasol).

[0038] Polymers containing maleic anhydride can be prepared by methods known to those skilled in the art, and then functionalized with a polyether mononuclear agent C and optionally a nonpolymeric nucleophile D by any method known in the art. For example, a polybasic acid can be prepared by esterification and / or amidation of a maleic anhydride-containing copolymer, or the maleic anhydride can be first esterified and / or amidated, and then polymerized with styrene and / or substituted styrene using any known polymerization technique or combination of polymerization techniques, employing bulk, solution, suspension, or emulsion methods to form a polybasic acid. Polymerization can include radical, anionic, cationic, atom-transfer, or group-transfer polymerization methods, or combinations thereof.

[0039] In the dispersants described herein, one or more maleic anhydride repeating units of A react with polyether nucleophile C and / or nonpolymeric nucleophile D to form one or more bonds, wherein these bonds are selected from (i) ester bonds formed by the reaction product of the alcohol group of polyether nucleophile C and / or nonpolymeric nucleophile D with the maleic anhydride repeating unit of A; (ii) salt bonds and / or amide bonds formed by the reaction product of the primary or secondary amine of polyether nucleophile C and / or nonpolymeric nucleophile D with the maleic anhydride repeating unit of A; or (iii) imide bonds formed by the reaction product of the primary amine group of polyether nucleophile C and / or nonpolymeric nucleophile D with the maleic anhydride repeating unit of A.

[0040] In another embodiment, polymeric intermediate P can be obtained by reacting a maleic anhydride-containing polymer (with a number-average molecular weight typically between 200 and 50,000 or 700 and 20,000) with a polyether mononuclear-philic reagent C and optionally a nonpolymeric nucleophilic reagent D, or can be obtained by reacting the above substances, optionally in the presence of a catalyst (such as an acid or base catalyst) and optionally with 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 molar number of A reacts with C; and 0% to 80%, or 0% to 50%, or 0% to 20%, or 0% of the total molar number of A reacts with D; provided that after the repeating unit A reacts 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 10%, or 0% to 5% of the A units are still able to remain in their anhydride form.

[0041] The dispersant used in this invention comprises a salt of P and X. X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof.

[0042] In some embodiments, the salt can be formed by using ammonia, an amine, a quaternary ammonium cation, or a pyridine cation as X. Examples of amines are methylamine, diethylamine, ethanolamine, diethanolamine, hexylamine, 2-ethylhexylamine, octadecylamine, 2-(dimethylamino)-2-methylprop-1-ol, 2-dimethylaminoethanol, and 2-amino-2-methyl-1-propanol. Quaternary ammonium cations can be either quaternary ammonium cations or benzyl ammonium cations. Quaternary ammonium cations may contain one or two alkyl groups having 6 to 20 carbon atoms. Examples of quaternary ammonium cations are tetraethylammonium, N-octadecyl-N,N,N-trimethylammonium; N,N-bisdodecyl-N,N-dimethylammonium, N-benzyl-N,N,N-trimethylammonium, and N-benzyl-N-octadecyl-N,N-dimethylammonium cations.

[0043] In other embodiments, the salt can be formed by using an alkali metal or an 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 can be used.

[0044] In another embodiment, X can be a polyamine, such as poly(ethyleneamine), alkylene polyamine, or polyallylamine or poly(C) 2-6(-alkylene imine), for example, in one embodiment, polyethylene imine. The polyamine or polyalkylene imine can be linear or branched. The number average molecular weight of the polyamine or polyalkylene imine can be from 140 g / mol to 100,000 g / mol; more ideally from 140 to 75,000; or preferably from 200 to 10,000 or 20,000. In some embodiments, each molecule of X can have a total of at least four primary amine groups and / or secondary amine groups, more ideally at least six primary amine groups and / or secondary amine groups.

[0045] Examples of polyamines that can be used as X in this invention may include, but are not limited to: amino-functionalized polyamino acids, such as polylysine purchased from Aldrich Chemical Co.; amino-functionalized silicones, which are marketed under trade names ASi2122 was purchased from Degussa AG; it is a polyamide, marketed under the trade name... or Dendritic compounds were purchased from Aldrich Chemical Co.; polyallylamine and poly(N-alkyl)allylamine, under the trade name PAA, were purchased from Nitto Boseki; polyvinylamine was purchased from Mitsubishi Kasei, under the trade name... Purchased from BASFAG; polyalkylene imides, such as polyethylimide, which are marketed under trade names Purchased from Nippon Shoku-bai Co., Ltd., and under the product name Purchased from BASF AG; and polypropylene imide, which is marketed under the trade name Purchased from DSM AG. Linear polyethylene imides can be prepared by hydrolysis of poly(N-acyl)alkylene imides, as described, for example, by Takeo Saegusa et al. in Macromolecules, 1972, Vol. 5, p. 4470. Polypropylene imide dendrites are commercially available from DSM Fine Chemicals, and poly(amide) dendrites are available as “Starburst” dendrites from Aldrich Chemical Company. Alkylene polyamines can be characterized as materials having less than 2%, typically less than 1% (by weight) of boiling points below about 200°C, and including vessel feet, such as ethylene polyamine vessel feet purchased from Dow Chemical Company (Freeport, Texas).

[0046] When X is polyimide, in one exemplary embodiment it is poly(C) 2-6 (-alkyleneimide) or polyethyleneimide (PEI). Polyimides can be linear, or especially branched.

[0047] In one embodiment, X comprises or is composed of an amine. In another embodiment, X may comprise a mixture of an amine and an alkali metal or alkaline earth metal, or a mixture of such metals. In some embodiments in which X comprises a mixture of an amine and a metal, the metal may be present in an amount of up to 50% by weight, or in some embodiments in an amount not exceeding 50% by weight or even not exceeding 40% by weight, or 30% by weight, or 25% by weight, or 20% by weight, or 10% by weight, or 5% by weight.

[0048] Since both P and X can have multiple co-reactive groups, in some cases, there may be more than one bond between them (as defined above). It is also generally accepted that more than one P can 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 also be a single P bonded to a single X.

[0049] In the dispersant used in this invention, polymer intermediate P and substance X react together, such that the -CO2H or -CO2 of P... - It reacts with the amine, metal, or other basic groups of X to produce ionic salt bonds and / or covalent bonds, or a mixture of ionic salt bonds 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.

[0050] In one embodiment, the reaction product or copolymer product of P and X can be present as a pure polymer or a polymer in an organic solvent. This can be achieved by dissolving the pure reaction product or copolymer product in a solvent, or by synthesizing 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.

[0051] The dispersions used in this 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 recognized categories of pigments described in the section entitled “Pigments” in the third edition and subsequent revisions of the Colour Index (1971) and its supplements. Examples of organic pigments include those derived from: azo, diazo, trizo, condensed azo, azo lakes, naphthol pigments, anthraquinones, anthraquinones, anthraquinones, benzimidazolones, carbazoles, pyrrolopyrrolediones, flavanones, indigo pigments, indanones, isodibenzoanthrones, isoyindanones, isoyindolones, isoyindolones, isoanthrone violet, metal complex pigments, oxazines, dinaphthalenes, violet ketones, pinanthrones, pyrazoloquinazolinones, quinacridones, quinophthalones, thioindigo, triarylcarbide pigments, triphenyldioxazines, xanthocyanins and phthalocyanine series, especially copper phthalocyanine and its nucleohalogenated derivatives, as well as lakes of acid dyes, basic dyes and mordant dyes. Carbon black, although strictly speaking an inorganic pigment, behaves more like an organic pigment in its dispersion properties. In one embodiment, the organic pigment is phthalocyanine (especially copper phthalocyanine), monoazo, diazo, indanone, anthraquinone, quinacridone, pyrrolopyrroledione, dinaphthalene, and carbon black.

[0052] Examples of inorganic pigments include metal oxides (such as titanium dioxide, rutile titanium dioxide, and surface-coated titanium dioxide), titanium oxides in various colors (such as yellow and black), iron oxides in various colors (such as yellow, red, brown, and black), zinc oxide, zirconium oxide, and 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), and pearlescent flakes (such as lead carbonate and bismuth oxychloride).

[0053] Inorganic solids include expanders and fillers, such as ground and 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, aluminum hydroperoxide or boehmite, calcium silicate and magnesium silicate, aluminosilicates (including nano-clay), kaolinite, montmorillonite (including bentonite, lithium montmorillonite and saponite), mica, talc (including muscovite, phlogopite) Mica, lepidolite, and chlorite), chalk, synthetic precipitated silica, pyrolytic silica, metal fibers and powders, zinc, aluminum, glass fibers, refractory fibers, carbon black (including single-walled and multi-walled carbon nanotubes, reinforced and unreinforced carbon black), graphite, buckyballs, bituminous materials, graphene, diamond, alumina, quartz, silica gel, wood flour, wood chips (including softwood and hardwood), sawdust, powdered paper / fibers, cellulose fibers (such as kenaf, hemp, sisal, flax, etc.). Cotton, cotton linters, jute, ramie, rice husks or bran, wine coconut, cattail reeds, coconut fiber, coconut shell fiber, oil palm fiber, kapok, banana leaves, calomel, fenugreek, agave fiber leaves, flax leaves, abaca, bagasse, rice straw, bamboo strips, wheat flour, MDF, etc.), vermiculite, zeolite, hydrotalcite, fly ash from power plants, incinerated sewage sludge ash, volcanic ash, blast furnace slag, asbestos, chrysotile, tremolite, crocidolite, wollastonite, palygorskite, etc., micro-particle ceramic materials. Materials (such as alumina, zirconium oxide, titanium dioxide, cerium dioxide, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, mixed silicon-aluminum nitrides and metal titanates); particulate magnetic materials, such as magnetic oxides of transition metals (typically iron and chromium), such as γ-Fe2O3, Fe3O4 and cobalt-doped iron oxides, ferrites (such as barium ferrites); and metal particles, such as aluminum, iron, nickel, cobalt, copper, silver, gold, palladium and platinum, and their alloys.

[0054] Other available solid materials include flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine, melamine cyanurate, antimony oxide, and borates.

[0055] In one specific embodiment of the invention, the pigment comprises or is composed of carbon black.

[0056] The dispersions of the present invention can be prepared by methods known and understood by those skilled in the art. In some embodiments, the dispersions used in the methods of the present invention comprise 0.5% to 40% by weight of pigment, 0.5% to 40% by weight of the dispersant described herein, and 20% to 99% by weight of 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 solely ethylene glycol. In another embodiment, the solvent is primarily or solely an ethylene glycol oligomer having 2 to 5 repeating ethylene glycol units.

[0057] In one embodiment, the dispersant used in the method of the present invention has a pH 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.

[0058] After preparing a dispersion comprising a solvent, a dispersant, and a pigment (all as described above), the method of the present invention further includes the step of adding a material with a boiling point above temperature (T) to the dispersion, wherein temperature (T) is the boiling point of the solvent. In one embodiment, the solvent comprises ethylene glycol or an ethylene glycol oligomer having 2 to 5 repeating units, or is composed of ethylene glycol or an ethylene glycol oligomer having 2 to 5 repeating units. In such embodiments, temperature T may be at least 180°C, or 190°C, or 195°C, or even at least 200°C. The substance with a boiling point above temperature (T) may include other solvents, but may also include reactive monomer components. In one specific embodiment, the substance with a boiling point above temperature (T) comprises a monomer formed from the reaction product of a lower aliphatic glycol with dimethyl terephthalate or the reaction product of a lower aliphatic glycol with terephthalic acid. The substance with a boiling point above temperature (T) may also include bis(2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or mixtures thereof.

[0059] After mixing a substance with a boiling temperature higher than (T) with the dispersion described herein, or simultaneously with mixing, the mixture is heated to a temperature of at least T or higher. In some embodiments, the mixture is heated to temperatures above 180°C, or 190°C, or 195°C, or 200°C, or even at least 250°C (e.g., 200°C to 300°C, or even 250°C to 295°C). The dispersant of the present invention unexpectedly provides a pigment dispersion stable at elevated temperatures.

[0060] In one embodiment, the present invention also provides a method for preparing a colored polymer, the method comprising the step of providing a pigment dispersion comprising (i) a solvent comprising or consisting of ethylene glycol; (ii) a dispersant comprising a salt of P and X; wherein P is a polyether-functionalized polyacid formed via a reaction of: (i) a polymer containing maleic anhydride, (ii) a polyether monophilic nucleophilic reagent C, and optionally, (iii) a nonpolymeric monophilic nucleophilic reagent D, and X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof. The preparation of each component and dispersant is as described above. The present invention also includes the use of the pigment dispersion in the manufacture of polymers, such as polyethylene terephthalate, wherein the pigment dispersion comprises a dispersant as described herein.

[0061] In one embodiment, the colored polymer prepared by the method of the present invention is polyethylene terephthalate (PET). Methods for preparing 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 method, monomers used to prepare the PET polymer are formed via 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 products of the transesterification or esterification reactions include bis(2-hydroxyethyl) terephthalate or 2-hydroxyethyl terephthalic acid. In one embodiment of the invention, the dispersion described herein is mixed with the product of an ester exchange or esterification reaction, and then heated to a temperature of at least 180°C, or at least 190°C, or at least 195°C, or at least 200°C, or even at least 250°C (e.g., 200°C to 300°C), or even 250°C to 295°C.

[0062] In one embodiment, the polymer prepared by the method of the present invention comprises 0.01% to 20% by weight of the polymer, further for example 0.1% to 2% by weight, or even 0.4% to 1.6% by weight. In one exemplary embodiment, the pigment comprises carbon black.

[0063] The following examples provide an illustration of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.

[0064] Example

[0065] A series of polymer intermediates (Z) were prepared as follows. :

[0066] Intermediate 1: Poly(styrene-co-maleic anhydride) (Xiran 2000P, Polyscope) (50.00 parts) and ethyl acetate (240.06 parts) were heated at 50°C for 0.5 hours. Polyetheramine (Surfonamine L-207) (310.09 parts) was added to a reaction vessel and heated at 70°C for 4 hours. The reaction was equipped with a solvent trap and heated at 80°C for 11.25 hours. The reaction was then heated at 90°C for 6.5 hours to obtain a clear yellow liquid. Acid value = 24.98 mg KOH g⁻¹, amine value = 1.66 mg KOH g⁻¹, active ingredient content = 100.00%.

[0067] Intermediate 2: Poly(styrene-co-maleic anhydride) (Xiran 2000P, Polyscope) (8.00 parts) and ethyl acetate (54.95 parts) were heated at 50°C for 1 hour. Polyetheramine (Surfonamine L-300) (74.42 parts) was added to a reaction vessel and heated at 70°C for 3.5 hours. The reaction was equipped with a solvent trap and heated at 80°C for 4 hours. The reaction was then heated at 90°C for 4.33 hours to obtain an opaque yellow solid. Acid value = 21.95 mg KOH g⁻¹, amine value = 2.21 mg KOH g⁻¹, active ingredient content = 100.00%.

[0068] 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°C for 1 hour. Polyetheramine (Surfonamine L-207) (42.30 parts) was added to the reaction vessel and heated at 110°C for 0.66 hours over a period of 0.5 hours. 3-(dimethylamino)-1-propylamine (2.08 parts) was added to the reaction vessel and heated at 130°C for 2 hours. The reaction was equipped with a solvent trap and heated at 170°C for 30 hours to obtain a clear, yellow, viscous liquid. Acid value = 8.19 mg KOH g⁻¹, amine value = 20.63 mg KOH g⁻¹, active ingredient content = 100.00%.

[0069] Intermediate 4: Poly(styrene-co-maleic anhydride) (Xiran 2000P, Polyscope) (12.51 parts) and ethyl acetate (52.13 parts) were heated at 50°C for 1 hour. Polyetheramine (Surfonamine L-207) (16.89 parts) was added to the reaction vessel and heated at 50°C for 3 hours. Polyethylene glycol monomethyl ether MW1000 (20.41 parts) was added to the reaction vessel and heated at 70°C for 19.5 hours. Phenylethylamine (1.24 parts) was added to the reaction vessel and heated at 70°C for 23 hours. The reaction was equipped with a solvent trap and heated at 85°C for 4.5 hours to obtain an opaque amber solid. Acid value = 38.77 mg KOH g⁻¹, amine value = 0 mg KOH g⁻¹, active ingredient content = 100.00%.

[0070] Intermediate 5: Poly(styrene-co-maleic anhydride) (Xiran EF60, Polyscope) (22.00 parts) and ethyl acetate (53.21 parts) were heated at 50°C for 20 minutes. Polyetheramine (Surfonamine L-207) (57.82 parts) was added to a reaction vessel and heated at 70°C for 4 hours. The reaction was equipped with a solvent trap and heated at 90°C for 13 hours to obtain a clear, brown, viscous liquid. Acid value = 21.99 mg KOH g⁻¹, amine value = 0 mg KOH g⁻¹, active ingredient content = 100.00%.

[0071] Intermediate 6: Poly(styrene-co-maleic anhydride) (Xiran 1000P, Polyscope) (13.00 parts) and ethyl acetate (54.22 parts) were heated at 50°C for 40 minutes. Polyetheramine (Surfonamine L-207) (64.29 parts) was added to a reaction vessel and heated at 70°C for 3 hours. Phenylethylamine (1.75 parts) and 1-decyl alcohol (2.29 parts) were added to a reaction vessel and heated at 70°C for 14.75 hours. The reaction was equipped with a solvent trap and heated at 90°C for 9.25 hours to obtain a clear brown liquid. Acid value = 37.11 mg KOH g⁻¹, amine value = 2.00 mg KOH g⁻¹, active ingredient content = 100.00%.

[0072] The following are examples of dispersant preparations or provided examples. The pH of the dispersant was measured using a 50% ethylene glycol solution of the dispersant:

[0073] Example 1: Intermediate 1 (25.00 parts) and ethylene glycol (27.50 parts) were heated at 60°C. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (2.50 parts) was added to the resulting mixture, and the mixture was heated for 0.25 hours to obtain a clear, pale yellow solution. Active ingredient content = 45.5%, pH = 9.

[0074] Example 2: Intermediate 1 (25.00 parts) and ethylene glycol (30.00 parts) were heated at 60°C. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (5.00 parts) was added to the resulting mixture, and the mixture was heated for 0.25 hours to obtain a clear, pale yellow solution. Active ingredient content = 40.9%, pH = 9.

[0075] Example 3: Intermediate 2 (40.00 parts) and ethylene glycol (44.00 parts) were heated at 60°C. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (4.00 parts) was added to the resulting mixture, and the mixture was heated for 0.5 hours to obtain a clear, pale yellow solution. Active ingredient content = 45.5%, pH = 9.

[0076] Example 4: Intermediate 3 (1.05 parts) and ethylene glycol (7.45 parts) were heated at 70°C. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (0.21 parts) was added to the resulting mixture, and the mixture was heated for 0.5 hours to obtain a clear, pale yellow solution. Active ingredient content = 11.97%, pH = 9.

[0077] Example 5: Intermediate 4 (1.05 parts) and ethylene glycol (7.45 parts) were heated at 70°C. 2-Dimethylamino-2-methylpropanol (80% aqueous solution) (0.21 parts) was added to the resulting mixture, and the mixture was heated for 0.5 hours to obtain a clear, pale yellow solution. Active ingredient content = 11.73%, pH = 9.

[0078] Example 6: Intermediate 1 (15.15 parts) and ethylene glycol (16.57 parts) were heated at 50°C. 2-Amino-2-methyl-1-propanol (95% aqueous solution) (1.52 parts) was added to the resulting mixture, and the mixture was heated for 0.50 hours to obtain a clear, colorless solution. Active ingredient content = 46.11%, pH = 9.

[0079] Example 7: Intermediate 5 (18.62 parts) and ethylene glycol (20.48 parts) were heated at 60°C. 2-(dimethylamino)-ethanol (1.86 parts) was added to the resulting mixture, and the mixture was heated for 0.25 hours to obtain a clear amber solution. Active ingredient content = 44.95%, pH = 8.

[0080] Example 8: Intermediate 6 (20.22 parts) and ethylene glycol (22.24 parts) were heated at 50°C. 2-(dimethylamino)ethanol (2.02 parts) was added to the resulting mixture, and the mixture was heated for 0.33 hours to obtain a clear brown solution. Active ingredient content = 44.44%, pH = 8.

[0081] Example 9: Intermediate 1 (33.81 parts) and ethylene glycol (37.19 parts) were heated at 50°C. Triethylamine (3.38 parts) was added to the resulting mixture, and the mixture was heated for 0.25 hours to obtain a clear yellow solution. Active ingredient content = 45.80%, pH = 9.

[0082] Comparative Example 1: Orotan SN(Dow)-Naphthalenesulfonic acid-formaldehyde condensate.

[0083] Comparative Example 2: Morwet D-809 (Nouryon)-Naphthalenesulfonic acid-formaldehyde condensate

[0084] Comparative Example 3: Intermediate 6

[0085] Experiment 1 - High Temperature Test 200°C: 1.05 g of the example or comparative example to be tested (100% active material excluding ethylene glycol or water, i.e., 2.10 g of 50% active material will be used) and 7.45 g of ethylene glycol (this value is reduced due to the amount of inactive material added as part of the example or comparative example, i.e., 6.40 g for 50% active material) were placed in a 32 mL vial and shaken until the sample was completely dissolved. Glass beads (17.00 g) and carbon black (Special Black 4, 1.50 g) were placed in the vial and the vial was sealed. The material was then ground on a horizontal shaker for 16 hours to produce a grinding base. The grinding base (1.00 g) was removed from the vial and placed in a 32 mL vial. Ethylene glycol (6.75 g) was added to the vial, and the contents were stirred until homogeneous to produce a diluted grinding base. The vial was heated to 200°C. Once the diluted grinding base reaches 200°C, it is inspected to determine its homogeneity. Heterogeneous materials have a much larger proportion of pigment at the bottom of the vial, while homogeneous materials are acceptable. The results are summarized in Table 1.

[0086] Table 1

[0087] Comparative Example 1 homogenization Comparative Example 2 homogenization Comparative Example 3 homogenization 1 homogenization 2 homogenization 3 homogenization 4 homogenization 5 homogenization 6 homogenization 7 homogenization 8 homogenization 9 homogenization

[0088] Experiment 2: Addition of a material with a boiling point higher than that of ethylene glycol solvent (bis(2-hydroxyethyl) terephthalate (“BHET”)) at 200°C: The material obtained from Experiment 1 was transferred to Experiment 2. 7.75 g of BHET was added to a vial at 200°C. Once the BHET melted, the sample was stirred and heated for another hour. This process was repeated twice more, resulting in a total addition of 23.25 g of BHET and a total heating time of 3 hours. The sample was then allowed to cool to room temperature. Once cooled, the sample was first examined to determine homogeneity, where heterogeneous samples either had black spots throughout, a layer of black material at the bottom, or both. Next, the color was determined. A homogeneous sample with a black color was acceptable. The results are summarized in Table 2.

[0089] Table 2

[0090] Comparative Example 1 heterogeneous grey Comparative Example 2 heterogeneous grey Comparative Example 3 homogenization grey 1 homogenization black 2 homogenization black 3 homogenization black 4 homogenization black 5 homogenization black 6 homogenization black 7 homogenization black 8 homogenization black 9 homogenization black

[0091] This experiment demonstrates that the pigment dispersion described herein can be used at elevated temperatures (e.g., the temperatures required for polymerizing PET polymers).

[0092] Each of the foregoing references is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. Reference to any document is not an admission that it is prior art or constitutes general knowledge to a person skilled in the art in any jurisdiction. Unless expressly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, etc., specified in this specification should be understood to be modified by the word “about.” It should be understood that the upper and lower limits of the quantities, ranges, and proportions described herein can be combined independently. Similarly, the ranges and quantities of each element of the invention can be used in conjunction with the ranges or quantities of any other element.

[0093] As used herein, the transitional term "comprising," synonymous with "comprising," "containing," or "characterized in," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every instance of "comprising" herein, it is intended that the term, as an alternative, narrower embodiment, also encompass the phrases "consistently composed of" and "composed of," wherein "composed of" excludes any unstated elements or steps, while "consistently composed of" allows the inclusion of additional, unlisted elements or steps that do not materially affect the essential and novel characteristics of the composition or method under consideration.

[0094] While certain representative embodiments and details have been shown to illustrate the purpose of this invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. In this respect, the scope of the invention is defined only by the following claims.

Claims

1. A method for preparing a colored polymer, the method comprising the following steps: (a) Providing a pigment dispersion, the pigment dispersion comprising: (i) a solvent, wherein the solvent comprises ethylene glycol or an ethylene glycol oligomer; (ii) A dispersant comprising a salt of P and X; wherein P is a polyether-functionalized polyacid intermediate formed by the reaction of the following substances: (i) a polymer containing maleic anhydride, (ii) a polyether monophilic nucleophile C, and (iii) optionally, a nonpolymeric monophilic nucleophile D, and X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof. (i) wherein the maleic anhydride-containing polymer has formula (A). n -(B) m -(E) q ; Where A is a maleic anhydride unit with the following structure: B is a styrene or substituted styrene unit having the following structure: Where R is H or CH3, R' is a halogen, a nitro group, or optionally a C1 to C2 group containing an oxygen atom. 10 Alkyl or aromatic groups, and e is 0 to 5; E is derived from a monounsaturated monomer containing 2 to 160 carbon atoms, which may optionally contain ethers, esters, amides, tertiary amines, acids, or halogens, but excludes alcohols, primary amines, and secondary amines; Where n is 10 to 50, m is 10 to 150, and q is 0 to 200, provided that the ratio of n to m is between 1:1 and 1:6; The polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% of all repeating units are ethylene glycol, and wherein the polyether monophilic nucleophilic reagent C comprises a single alcohol, primary amine, or secondary amine group; wherein the nonpolymeric monophilic nucleophilic reagent D is a straight-chain or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms, and comprises a single alcohol, primary amine, or secondary amine group, and optionally one or more tertiary amine, halide, or nitro groups, provided that D does not contain acid groups; And 10% to 100% of the total moles of A react with C; and 0% to 80% of the total moles of A react with D; provided that after the repeating unit A reacts with C and D, at least 20% of A must contain carboxylic acid groups, and no more than 10% of the A units can still be in their anhydride form. (iii) Pigments; (b) Provide a diacid or diester monomer; (c) Mixing the monomer with the pigment dispersion; and (d) Heating the mixture of the monomer and the pigment dispersion to at least 180°C.

2. The method according to claim 1, wherein E is derived from a monounsaturated monomer comprising 2 to 45 carbon atoms.

3. The method of claim 1, wherein the polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 70% of all repeating units are ethylene glycol.

4. The method according to claim 1, wherein 30% to 100% of the total moles of A react with C.

5. The method according to claim 1, wherein 50% to 100% of the total moles of A react with C.

6. The method according to claim 1, wherein 70% to 100% of the total moles of A react with C.

7. The method according to claim 1, wherein 0% to 50% of the total moles of A react with D.

8. The method according to claim 1, wherein 0% to 25% of the total moles of A react with D.

9. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 30% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

10. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 40% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

11. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 50% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

12. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 60% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

13. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 70% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

14. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 80% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

15. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 90% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

16. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and 0% to 10% of the A units are still able to remain in their anhydride form.

17. The method of claim 1, wherein the condition is that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and 0% to 5% of the A units are still able to remain in their anhydride form.

18. The method of claim 1, wherein the mixture of the monomer and the pigment dispersion is heated to at least 190°C.

19. The method of claim 1, wherein the mixture of the monomer and the pigment dispersion is heated to at least 195°C.

20. The method of claim 1, wherein the mixture of the monomer and the pigment dispersion is heated to at least 200°C.

21. The method of claim 1, wherein the mixture of the monomer and the pigment dispersion is heated to at least 250°C.

22. The method of claim 1, wherein the weight ratio of P to X is 30:1 to 1:

1.

23. The method of claim 1, wherein the weight ratio of P to X is 15:1 to 1:

1.

24. The method according to any one of claims 1 to 23, wherein E comprises a repeating (meth)acrylic acid unit having the following structure: Where R is H or CH3, and R1 is a C1 to C1 group containing two heteroatoms. 10 Alkyl or aromatic groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers.

25. The method according to any one of claims 1 to 23, wherein E comprises a (meth)acrylamide repeating unit having the following structure: Where R is H or CH3, and R2 and R3 are each independently H or C1 to C containing heteroatoms. 20 Alkyl or aryl groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers, provided that R2 and R3 cannot both be H.

26. The method according to any one of claims 1 to 23, wherein E comprises a (meth)acrylamide repeating unit having the following structure: Where R is H or CH3, and R2 and R3 are linked together to form C2 to C3. 16 Cyclic groups.

27. The method according to any one of claims 1 to 23, wherein E comprises a vinyl repeating unit having the following structure: Where R is H or CH3, and R4 is H or optionally contains heteroatoms or halides from C1 to C4. 20 Alkyl or aryl groups, or MW is 150 to 3000 and is C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers.

28. The method of claim 27, wherein the heteroatom is oxygen.

29. The method of claim 24, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R1 comprises MW being 150 to 3000 and having a carbon content of C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

30. The method of claim 25, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R2, R3 comprise MW of 150 to 3000 and are C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

31. The method of claim 26, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R2, R3 comprise MW of 150 to 3000 and are C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

32. The method of claim 27, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R4 comprises MW being 150 to 3000 and having a carbon content of C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

33. The method according to any one of claims 1 to 23, wherein X is an amine.

34. The method according to any one of claims 1 to 23, wherein X comprises an amine and a mixture of alkali metals and / or alkaline earth metals, and wherein the alkali metals and / or alkaline earth metals account for no more than 50% by weight of X.

35. The method of claim 34, wherein the alkali metal and / or alkaline earth metal constitutes no more than 40% by weight of X.

36. The method of claim 34, wherein the alkali metal and / or alkaline earth metal constitutes no more than 30% by weight of X.

37. The method of claim 34, wherein the alkali metal and / or alkaline earth metal constitutes no more than 20% by weight of X.

38. The method of claim 34, wherein the alkali metal and / or alkaline earth metal constitutes no more than 10% by weight of X.

39. The method according to any one of claims 1 to 23, wherein the pigment comprises carbon black.

40. The method according to any one of claims 1 to 23, wherein the solvent comprises ethylene glycol.

41. The method according to any one of claims 1 to 23, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

42. The method according to any one of claims 1 to 23, wherein the dispersion comprises 0.5% to 40% by weight of pigment, 0.5% to 40% by weight of dispersant, and 20% to 99% by weight of solvent.

43. The method according to any one of claims 1 to 23, wherein the monomer comprises bis(2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or a mixture thereof.

44. The method of claim 42, wherein the monomer comprises bis(2-hydroxyethyl) terephthalate.

45. The method of claim 42, wherein the monomer comprises 2-hydroxyethyl terephthalic acid.

46. ​​The method according to any one of claims 1 to 23, wherein the monomer comprises the reaction product of dimethyl terephthalate and a lower aliphatic diol, or the reaction product of terephthalic acid and a lower aliphatic diol.

47. The method of claim 46, wherein the lower aliphatic diol comprises ethylene glycol.

48. The method according to any one of claims 1 to 23, wherein the polymer is polyethylene terephthalate.

49. The method according to any one of claims 1 to 23, wherein the pigment is composed of carbon black.

50. The method according to any one of claims 1 to 23, wherein the solvent is composed of ethylene glycol.

51. The method according to any one of claims 1 to 23, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

52. The method according to claim 42, wherein the monomer comprises bis(2-hydroxyethyl) terephthalate.

53. The method according to claim 42, wherein the monomer is composed of 2-hydroxyethyl terephthalic acid.

54. The method according to any one of claims 1 to 23, wherein the monomer comprises the reaction product of dimethyl terephthalate and a lower aliphatic diol.

55. The method according to any one of claims 1 to 23, wherein the monomer comprises the reaction product of terephthalic acid and a lower aliphatic diol.

56. The method of claim 46, wherein the lower aliphatic diol is composed of ethylene glycol.

57. The method of claim 1, wherein the solvent is composed of ethylene glycol or an ethylene glycol oligomer.

58. Use of pigment dispersions in the manufacture of polymers, wherein the polymer is polyethylene terephthalate, and wherein the pigment dispersion comprises: Solvent, wherein the solvent comprises or is composed of ethylene glycol or ethylene glycol oligomers; Pigments; and A dispersant comprising a salt of P and X; wherein P is a polyether-functionalized polyacid intermediate formed by the reaction of the following substances: (i) a polymer containing maleic anhydride, (ii) a polyether monophilic nucleophile C, and (iii) optionally, a nonpolymeric monophilic nucleophile D, and X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof. (i) wherein the maleic anhydride-containing polymer has formula (A). n -(B) m -(E) q ; Where A is a maleic anhydride unit with the following structure: B is a styrene or substituted styrene unit having the following structure: Where R is H or CH3, R' is a halogen, a nitro group, or optionally a C1 to C2 group containing an oxygen atom. 10 Alkyl or aromatic groups, and e is 0 to 5; E is derived from a monounsaturated monomer containing 2 to 160 carbon atoms, which may optionally contain ethers, esters, amides, tertiary amines, acids, or halogens, but excludes alcohols, primary amines, and secondary amines; Where n is 10 to 50, m is 10 to 150, and q is 0 to 200, provided that the ratio of n to m is between 1:1 and 1:6; The polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% of all repeating units are ethylene glycol, and wherein the polyether monophilic nucleophilic reagent C comprises a single alcohol, primary amine, or secondary amine group; wherein the nonpolymeric monophilic nucleophilic reagent D is a straight-chain or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms, and comprises a single alcohol, primary amine, or secondary amine group, and optionally one or more tertiary amine, halide, or nitro groups, provided that D does not contain acid groups; And 10% to 100% of the total moles of A react with C; and 0% to 80% of the total moles of A react with D; provided that after the repeating unit A reacts with C and D, at least 20% of A must contain carboxylic acid groups, and no more than 10% of the A units can still be in their anhydride form.

59. The use according to claim 58, wherein E is derived from a monounsaturated monomer comprising 2 to 45 carbon atoms.

60. The use according to claim 58, wherein the polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 70% of all repeating units are ethylene glycol.

61. The use according to claim 58, wherein 30% to 100% of the total moles of A react with C.

62. The use according to claim 58, wherein 50% to 100% of the total moles of A react with C.

63. The use according to claim 58, wherein 70% to 100% of the total moles of A react with C.

64. The use according to claim 58, wherein 0% to 50% of the total moles of A react with D.

65. The use according to claim 58, wherein 0% to 25% of the total moles of A react with D.

66. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 30% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

67. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 40% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

68. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 50% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

69. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 60% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

70. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 70% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

71. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 80% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

72. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 90% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

73. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and 0% to 10% of the A units are still able to remain in their anhydride form.

74. The use according to claim 58, wherein the condition is that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and 0% to 5% of the A units are still able to remain in their anhydride form.

75. The use according to claim 58, wherein the weight ratio of P to X is 30:1 to 1:

1.

76. The use according to claim 58, wherein the weight ratio of P to X is 15:1 to 1:

1.

77. The use according to claim 58, wherein E comprises a repeating (meth)acrylic acid unit having the following structure: Where R is H or CH3, and R1 is a C1 to C1 group containing two heteroatoms. 10 Alkyl or aromatic groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers.

78. The use according to claim 58, wherein E comprises a (meth)acrylamide repeating unit having the following structure: Where R is H or CH3, and R2 and R3 are each independently H or C1 to C containing heteroatoms. 20 Alkyl or aryl groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers, provided that R2 and R3 cannot both be H.

79. The use according to claim 58, wherein E comprises a (meth)acrylamide repeating unit having the following structure: Where R is H or CH3, and R2 and R3 are linked together to form C2 to C3. 16 Cyclic groups.

80. The use according to claim 58, wherein E comprises a vinyl repeating unit having the following structure: Where R is H or CH3, and R4 is H or optionally contains heteroatoms or halides from C1 to C4. 20 Alkyl or aryl groups, or MW is 150 to 3000 and is C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers.

81. The use according to claim 77, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R1 comprises MW being 150 to 3000 and having C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

82. The use according to claim 78, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R2, R3 comprise MW of 150 to 3000 and of C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

83. The use according to claim 79, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R2, R3 comprise MW of 150 to 3000 and of C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

84. The use according to claim 80, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R4 comprises MW being 150 to 3000 and having C1 to C2 atoms. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

85. The use according to claim 58, wherein X is an amine.

86. The use according to claim 58, wherein X comprises an amine and a mixture of alkali metals and / or alkaline earth metals, and wherein the alkali metals and / or alkaline earth metals constitute no more than 50% by weight of X.

87. The use according to claim 86, wherein the alkali metal and / or alkaline earth metal constitutes no more than 40% by weight of X.

88. The use according to claim 86, wherein the alkali metal and / or alkaline earth metal constitutes no more than 30% by weight of X.

89. The use according to claim 86, wherein the alkali metal and / or alkaline earth metal constitutes no more than 20% by weight of X.

90. The use according to claim 86, wherein the alkali metal and / or alkaline earth metal constitutes no more than 10% by weight of X.

91. The use according to claim 58, wherein the pigment comprises carbon black.

92. The use according to claim 58, wherein the pigment is composed of carbon black.

93. The use according to claim 58, wherein the solvent comprises ethylene glycol.

94. The use according to claim 58, wherein the solvent is composed of ethylene glycol.

95. The use according to claim 58, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 repeating ethylene glycol units.

96. The use according to claim 58, wherein the solvent comprises an ethylene glycol oligomer having 2 to 5 repeating ethylene glycol units.

97. The use according to claim 58, wherein the dispersion comprises 0.5% to 40% by weight of pigment, 0.5% to 40% by weight of dispersant, and 20% to 99% by weight of solvent.

98. The use according to claim 80, wherein the heteroatom is oxygen.

99. Use of pigment dispersions in the manufacture of polyethylene terephthalate, wherein the pigment dispersion comprises: Ethylene glycol; Pigments; and A dispersant comprising a salt of P and X; wherein P is a polyether-functionalized polyacid intermediate formed by the reaction of the following substances: (i) a polymer containing maleic anhydride, (ii) a polyether monophilic nucleophile C, and (iii) optionally, a nonpolymeric monophilic nucleophile D, and X is an alkali metal, an alkaline earth metal, ammonia, an amine, or a mixture thereof. (i) wherein the maleic anhydride-containing polymer has formula (A). n -(B) m -(E) q ; Where A is a maleic anhydride unit with the following structure: B is a styrene or substituted styrene unit having the following structure: Where R is H or CH3, R' is a halogen, a nitro group, or optionally a C1 to C2 group containing an oxygen atom. 10 Alkyl or aromatic groups, and e is 0 to 5; E is derived from a monounsaturated monomer containing 2 to 160 carbon atoms, which may optionally contain ethers, esters, amides, tertiary amines, acids, or halogens, but excludes alcohols, primary amines, and secondary amines; Where n is 10 to 50, m is 10 to 150, and q is 0 to 200, provided that the ratio of n to m is between 1:1 and 1:6; The polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 50% of all repeating units are ethylene glycol, and wherein the polyether monophilic nucleophilic reagent C comprises a single alcohol, primary amine, or secondary amine group; wherein the nonpolymeric monophilic nucleophilic reagent D is a straight-chain or branched, saturated or unsaturated alkyl or aryl chain having 1 to 22 carbon atoms, and comprises a single alcohol, primary amine, or secondary amine group, and optionally one or more tertiary amine, halide, or nitro groups, provided that D does not contain acid groups; And 10% to 100% of the total moles of A react with C; and 0% to 80% of the total moles of A react with D; provided that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and no more than 10% of the A units can still be in their anhydride form, wherein the polyethylene terephthalate is a reaction product of ethylene glycol and a monomer selected from bis(2-hydroxyethyl) terephthalate, 2-hydroxyethyl terephthalic acid, or mixtures thereof.

100. The use according to claim 99, wherein E is derived from a monounsaturated monomer comprising 2 to 45 carbon atoms.

101. The use according to claim 99, wherein the polyether monophilic nucleophilic reagent C comprises 6 to 70 ethylene glycol repeating units, and optionally comprises propylene glycol repeating units and / or butanediol repeating units, provided that at least 70% of all repeating units are ethylene glycol.

102. The use according to claim 99, wherein 30% to 100% of the total moles of A react with C.

103. The use according to claim 99, wherein 50% to 100% of the total moles of A react with C.

104. The use according to claim 99, wherein 70% to 100% of the total moles of A react with C.

105. The use according to claim 99, wherein 0% to 50% of the total moles of A react with D.

106. The use according to claim 99, wherein 0% to 25% of the total moles of A react with D.

107. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 30% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

108. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 40% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

109. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 50% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

110. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 60% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

111. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 70% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

112. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 80% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

113. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 90% of A must contain a carboxylic acid group, and no more than 10% of the A units are still able to remain in their anhydride form.

114. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and 0% to 10% of the A units are still able to remain in their anhydride form.

115. The use according to claim 99, wherein the condition is that after the repeating unit A reacts with C and D, at least 20% of A must contain a carboxylic acid group, and 0% to 5% of the A units are still able to remain in their anhydride form.

116. The use according to claim 99, wherein the weight ratio of P to X is 30:1 to 1:

1.

117. The use according to claim 99, wherein the weight ratio of P to X is 15:1 to 1:

1.

118. The use according to claim 99, wherein E comprises a repeating (meth)acrylic acid unit having the following structure: Where R is H or CH3, and R1 is a C1 to C1 group containing two heteroatoms. 10 Alkyl or aromatic groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers.

119. The use according to claim 99, wherein E comprises a (meth)acrylamide repeating unit having the following structure: Where R is H or CH3, and R2 and R3 are each independently H or C1 to C containing heteroatoms. 20 Alkyl or aryl groups, or a weight-average molecular weight (MW) of 150 to 3000 and C1 to C2. 20 Alkyl-terminated ethylene oxide polyethers and / or propylene oxide polyethers, provided that R2 and R3 cannot both be H.

120. The use according to claim 99, wherein E comprises a (meth)acrylamide repeating unit having the following structure: Where R is H or CH3, and R2 and R3 are linked together to form C2 to C3. 16 Cyclic groups.

121. The use according to claim 99, wherein E comprises a vinyl repeating unit having the following structure: Where R is H or CH3, and R4 is H or optionally contains heteroatoms or halides from C1 to C4. 20 Alkyl or aryl groups, or MW is 150 to 3000 and is C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers.

122. The use according to any one of claims 118, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R1 comprises MW being 150 to 3000 and having C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

123. The use according to claim 119, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R2, R3 comprise MW of 150 to 3000 and of C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

124. The use according to claim 120, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R2, R3 comprise MW of 150 to 3000 and of C1 to C2. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

125. The use according to claim 121, wherein E is derived from a monounsaturated monomer having 2 to 45 carbon atoms, and wherein R4 comprises MW being 150 to 3000 and having C1 to C2 atoms. 20 Cyclic group-terminated ethylene oxide polyethers and / or propylene oxide polyethers, or compositions thereof, wherein the carbon atoms in the polyethers are carbon atoms other than those in the monounsaturated monomers.

126. The use according to claim 99, wherein X is an amine.

127. The use according to claim 99, wherein X comprises an amine and a mixture of alkali metals and / or alkaline earth metals, and wherein the alkali metals and / or alkaline earth metals constitute no more than 50% by weight of X.

128. The use according to claim 127, wherein the alkali metal and / or alkaline earth metal constitutes no more than 40% by weight of X.

129. The use according to claim 127, wherein the alkali metal and / or alkaline earth metal constitutes no more than 30% by weight of X.

130. The use according to claim 127, wherein the alkali metal and / or alkaline earth metal constitutes no more than 20% by weight of X.

131. The use according to claim 127, wherein the alkali metal and / or alkaline earth metal constitutes no more than 10% by weight of X.

132. The use according to claim 99, wherein the pigment comprises carbon black.

133. The use according to claim 99, wherein the pigment is composed of carbon black.

134. The use according to claim 99, wherein the pigment dispersion further comprises an additional solvent comprising an ethylene glycol oligomer having 2 to 5 ethylene glycol repeating units.

135. The use according to claim 99, wherein the dispersion comprises 0.5% to 40% by weight of pigment, 0.5% to 40% by weight of dispersant, and 20% to 99% by weight of solvent.

136. The use according to claim 121, wherein the heteroatom is oxygen.

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