WO2022132470A1 - Procédé de production d'un polymère à l'aide d'une dispersion de pigment - Google Patents

Procédé de production d'un polymère à l'aide d'une dispersion de pigment Download PDF

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Publication number
WO2022132470A1
WO2022132470A1 PCT/US2021/061932 US2021061932W WO2022132470A1 WO 2022132470 A1 WO2022132470 A1 WO 2022132470A1 US 2021061932 W US2021061932 W US 2021061932W WO 2022132470 A1 WO2022132470 A1 WO 2022132470A1
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Prior art keywords
polyether
mono
recited
ethylene glycol
amine
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PCT/US2021/061932
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English (en)
Inventor
Jonathan Burt
Elliot COULBECK
Le-yang ZHANG
Andrew J. Shooter
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Lubrizol Advanced Materials, Inc.
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Priority to CN202180084908.3A priority Critical patent/CN116568724A/zh
Publication of WO2022132470A1 publication Critical patent/WO2022132470A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the disclosed technology relates to a method of producing a pigmented polymer using a pigment dispersion which is stable at elevated temperatures.
  • the present invention relates to a method of producing a polymer using a pigment dispersion that is stable at elevated temperatures, comprising the steps of (1) providing a pigment dispersion containing (a) a solvent, having a boiling temperature (T), wherein the solvent comprises or consists of ethylene glycol or oligomers of ethylene glycol, (b) a pigment, for example, carbon black, and (c) a dispersant, (2) adding a material having a boiling point higher than temperature (T), and (3) heating the dispersion to at least the boiling temperature (T) of the solvent.
  • a pigment dispersion containing (a) a solvent, having a boiling temperature (T), wherein the solvent comprises or consists of ethylene glycol or oligomers of ethylene glycol, (b) a pigment, for example, carbon black, and (c) a dispersant, (2) adding a material having a boiling point higher than temperature (T), and (3) heating the dispersion to at least the boiling temperature (T) of the solvent.
  • the dispersant used in the present invention comprises a salt of P and X.
  • P is a polyether functionalized polyacid intermediate formed via the reaction of (i) a maleic anhydride containing polymer, (ii) polyether mono-nucleophile C, and (iii) optionally a non-polymeric mono-nucleophile D.
  • X may be an alkali metal, an alkaline earth metal, ammonia, an amine or mixtures thereof.
  • maleic anhydride containing polymer has the formula (A) n -(B) m -(E) q , where.
  • A is a maleic anhydride unit having the structure
  • B is a vinyl benzene or substituted vinyl benzene unit having the structure where R is H or CH3, preferably H, and R' is a halogen, a nitro (NO2) group, or a Ci to C10 alkyl or aromatic group optionally containing oxygen atoms, and e is 0 to 5, for example 1 to 5, or 0, and E is derived from a mono-unsaturated monomer containing 2 to 45 carbon atoms which may optionally contain ethers, esters, amides, tertiary amines, acids, halogens, but does not contain alcohols, primary amines, or secondary amines.
  • n 10 to 50
  • m 10 to 150
  • q is 0 to 200, preferably 0, with the proviso that the ratio of n to m is between 1 : 1 and 1 :6.
  • Polyether mono-nucleophile C contains 6 to 70 ethylene glycol repeat units, and, optionally, contains propylene glycol and/or butylene glycol repeat units, with the proviso that at least 50%, or at least 70% of all repeat units are ethylene glycol.
  • the poly ether mono-nucleophile C contain 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 1 to 22 carbon atoms and contains a single alcohol, primary amine, or secondary amine group and optionally one or more tertiary amine, halide, or nitro groups with the proviso that D is substantially free of or free of acid groups.
  • polyether functionalized polyacid P 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; with the proviso 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 a carboxylic acid group after repeat unit A is reacted with C and D, and no more than 10%, or 0 to 10%, or 0 to 5% of A units can still be in their anhydride form;
  • the present invention also includes the use of the dispersant described above to provide a stable pigment dispersion at elevated temperatures.
  • hydrocarbyl in this specification will mean hydrocarbon like and can include up to one oxygen or nitrogen for every four carbon atoms in the group, but preferably is just carbon and hydrogen atoms.
  • Hydro- carbylene will mean hydrocarbon with two hydrogen atoms removed. Hydro- carbylene will also optionally include up to one oxygen or nitrogen atom for every two carbon atoms in the group, but preferably is just carbon and hydrogen.
  • the present invention relates to a method of forming a pigment dispersion that is stable at elevated temperatures.
  • the method comprises the steps of (1) preparing a dispersion containing (a) a solvent, having a boiling temperature (T), wherein the solvent comprises or consists of ethylene glycol or oligomers of ethylene glycol, (b) a pigment, and (c) a dispersant, (2) adding a material having a boiling point higher than temperature (T), and (3) heating the dispersion to a temperature that is at least the boiling temperature (T) of the solvent.
  • T boiling temperature
  • the invention also includes the use of a dispersant to provide a stable pigment dispersion at elevated temperatures.
  • the solvent used in the present invention comprises ethylene glycol or oligomers of ethylene glycol or mixtures thereof.
  • the solvent comprises or consists of ethylene glycol.
  • the solvent comprises or consists of oligomers of ethylene glycol.
  • the oligomers may comprise 2 to 5 repeat units of ethylene glycol. If the dispersion used in the present invention contains one or more other co-solvents, these solvents may be selected from water, alkanols, alkane carboxylic acids and esters of alkane carboxylic acids among other solvents known to those skilled in the art.
  • 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.
  • ethylene glycol has a boiling temperature of 197 °C.
  • the boiling temperature refers to the initial boiling temperature, or the temperature at which any of the components of a mixture boil.
  • the dispersant used in the present invention comprises a salt of P and X.
  • P is a polyether functionalized polyacid intermediate formed via the reaction of (i) a maleic anhydride containing polymer, (ii) polyether mono-nucleophile C, and (iii) optionally a non-polymeric mono-nucleophile D.
  • X is an alkali metal, an alkaline earth metal, ammonia, an amine or mixtures thereof.
  • the maleic anhydride containing polymer has the formula (A) n -(B) m - (E).
  • A is a maleic anhydride unit having the structure
  • B is a vinyl benzene or substituted vinyl benzene unit having the structure where R is H or CEE, preferably H, R' is a halogen, a nitro (NO2) group, or a Ci to C10 alkyl or aromatic group optionally containing oxygen atoms.
  • the variable e may be 0 to 5, for example 1 to 5, or 0.
  • E is derived from a mono-unsaturated 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 does not contain alcohols, primary amines, or secondary amines.
  • E comprises, for example, a (meth)acrylic repeat unit having the structure where R is H or CH3, preferably H, and Ri is a Ci to C10 alkyl or aromatic group optionally including two hetero atoms or a polyether of ethylene and/or propylene oxide with a weight average molecular weight (MW) of 150 to 3000 and terminating in a Ci to C20 alkyl group.
  • E comprises, for example, a (meth)acrylamide unit having the structure where R is H or CH3, R2 and R3 are each independently H or a Ci to C20 alkyl or aryl group including a heteroatom, or a polyether of ethylene and/or propylene oxide with a weight average molecular weight (MW) of 150 to 3000 terminating in a Ci to C20 alkyl group, with the proviso that both R2 and R3 cannot both be H.
  • E comprises, for example, a (meth)acrylamide repeat unit having the structure where R is H or CEE and R2 and R3 are connected together to form a C2 to Ci6 cyclic group.
  • E comprises, for example, a vinyl repeat unit having the structure where R is H or CH3, and R4 is H or Ci to C20 alkyl or aryl group optionally including hetero atoms such as oxygen or halides, or a polyether of ethylene and/or propylene oxide with a MW of 150 to 3000 and terminating in a Ci to C20 cyclic group.
  • R is H or CH3, and R4 is H or Ci to C20 alkyl or aryl group optionally including hetero atoms such as oxygen or halides, or a polyether of ethylene and/or propylene oxide with a MW of 150 to 3000 and terminating in a Ci to C20 cyclic group.
  • R is H or CH3
  • R4 is H or Ci to C20 alkyl or aryl group optionally including hetero atoms such as oxygen or halides
  • a polyether of ethylene and/or propylene oxide with a MW of 150 to 3000 and terminating in a Ci to C20 cycl
  • n 10 to 50
  • m 10 to 150
  • q 0 to 200
  • the units A, B, and E may be arranged in a statistical or random architecture or they may have a block architecture, wherein (E) q forms one block and the combination of (A) n (B) m together forms the other block. These two blocks can be arranged in any combination and repeated throughout P.
  • Polyether mono-nucleophile C contains 6 to 70 ethylene glycol repeat units, and, optionally, contains propylene glycol and/or butylene glycol repeat units, with the proviso that at least 50%, or at least 70% of all repeat units are ethylene glycol. In one embodiment, C contains from 1 to 15 or even 1 to 10 propylene glycol repeat units.
  • the polyether mono-nucleophile C also contains a single alcohol, primary amine, or secondary amine group.
  • Polyether mono-nucleophile may be derived from a poly(alkyleneox- ide) monoalkyl ether monoamine.
  • Exemplary monoamine compounds of this type are commercially available as the Surfonamine® or JeffamineTM amines from Huntsman Corporation. Specific examples of Surfonamine® amines are L-100 (propylene oxide to ethylene oxide mole ratio of 3: 19), L-207 (propylene oxide to ethylene oxide mole ratio of 10:33), L-200 (propylene oxide to ethylene oxide mole ratio of4:41), L-300 (propylene oxide to ethylene oxide mole ratio of 8:58).
  • C may be derived from a poly(alkyleneoxide) monoalkyl ether.
  • These mono-alkyl ethers are available 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 1 to 22 carbon atoms and contains a single alcohol, primary amine, or secondary amine group and optionally one or more tertiary amine, halide, or nitro groups with the proviso that D is substantially free of or free of acid groups.
  • the primary amine may include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2- ethylhexyl amine, nonylamine, decylamine, undecylamine, dodecylamine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, or mixtures thereof.
  • the amine may include benzyl amine, 2-phenylethanamine (often referred to as phenylethyl amine), 3- phenylpropanamine, 4-phenylbutanamine, or mixtures thereof.
  • the primary amine may include benzyl amine or 2- phenyl ethanamine.
  • the primary amine may include 2-phenylethanamine.
  • the secondary amine may be, for example, dimethyl amine, diethyl amine, dipropyl amine, dibutyl amine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, N,N-diisopropylamine, N,N- diisobutylamine, diisoamylamine, piperidine, N,N-dimethylpiperidin-4-amine, N,N- dibenzylamine, N-benzylmethylamine, N-phenyl-N-propylamine, N-methyl-phene- thylamine, N-methyl-N-(l-phenylethyl)amine, 4-Bromo-N-methylbenzylamine, or 4-Fluoro-N-methylbenzylamine.
  • Suitable mono-functional nucleophiles D containing a hydroxyl functionality include alcohols with optionally substituted Cl-22 hy- drocarbylene groups such as methanol, ethanol, propan- l-ol, propan-2-ol, butanol, isobutanol, neopentyl alcohol, hexanol, octan-l-ol, 2-ethylhexanol, decanol, dodecanol, oleyl alcohol, stearyl alcohol, behenyl alcohol, cyclohexanol, benzyl alcohol, phenol, octylphenol, nonylphenol, phenylethanol, fluorinated alcohols such as lH,lH,2H,2H-perfluoro-l-decanol, C8-22 branched alcohols available under the trademark IsofolTM (ex Sasol).
  • the maleic anhydride containing polymer may be prepared by processes known to a skilled person and functionalized with the polyether mono-nucle- ophile C and, optionally, non-polymeric nucleophile D, by any method known in the art.
  • the polyacid may be prepared by esterification and/or amidation maleic anhydride containing copolymer, or the maleic anhydride can first be esteri- fied and/or amidated and then polymerized with vinyl benzene and/or substituted vinyl benzene to form the polyacid by any known polymerization technique or a combination of polymerization techniques using a bulk, solution, suspension or emulsion process.
  • the polymerization may comprise of a radical, anionic, cationic, atom transfer or group transfer polymerization process or combinations thereof.
  • one or more of the maleic anhydride repeat units of A react with, polyether nucleophile C and/or non-polymeric nucleophile D to form one or more bonds, where the bonds are selected from (i) an ester bond formed from the reaction product of an alcohol group of polyether nucleophile C and/or non-polymeric nucleophile D with a maleic anhydride of repeat unit of A; (ii) salt bonds and/or amide bonds formed from the reaction product of a primary or secondary amine of polyether nucleophile C and/or non-polymeric nucleophile D with a maleic anhydride repeat unit of A; or (iii) imide bonds formed from the reaction product of a primary amine group of polyether nucleophile C and/or non-polymeric nucleophile D with a maleic anhydride
  • the polymer intermediate P may be obtained or obtainable by reacting maleic anhydride containing polymer (typically with a number average molecular weight between 200 to 50,000, or 700 to 20,000) with polyether mono-nucleophile C and, optionally, non-polymeric nucleophile D, optionally in the presence of a catalyst, such as an acid or base catalyst, optionally using an appropriate solvent.
  • a catalyst such as an acid or base catalyst
  • 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; with the proviso 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 a carboxylic acid group after repeat unit A is reacted with C and D, and no more than 10%, or 0 to 10%, or 0 to 5% of A units can still be in their anhydride form.
  • the dispersant used in the present invention comprises a salt of P and X.
  • X is an alkali metal, an alkaline earth metal, ammonia, an amine or mixtures thereof.
  • the salt may be formed by using ammonia, an amine, quaternary ammonium or pyridinium cation as X.
  • amines are methylamine, diethylamine, ethanolamine, diethanolamine, hexylamine, 2-ethylhex- ylamine, octadecylamine, 2-(Dimethylamino)-2-methylpropan-l-ol, 2-dimethylami- noethanol and 2-amino-2-methyl-l -propanol.
  • the quaternary ammonium cation may be a quaternary ammonium cation or a benzalkonium cation.
  • the quaternary ammonium cation may contain one or two alkyl groups containing from 6 to 20 carbon atoms.
  • Examples of quaternary ammonium cations are tetraethyl ammonium, N- octadecyl-N,N,N-trimethyl ammonium; N,N-didodecyl-N,N-dimethyl ammonium, N-benzyl-N,N,N-trimethyl ammonium and N-benzyl-N-octadecyl-N,N-dimethyl ammonium cation.
  • the salt may be formed by using an alkali metal or alkaline earth metal as X.
  • an alkali metal or alkaline earth metal for example, monovalent alkali metals (Li, Na, K, Rb, Cs, and Fr) or divalent alkaline earth metals (Be, Mg, Ca, Sr, Ba, and Ra) may be used.
  • lithium, sodium and potassium may be used.
  • X can be a polyamine such as poly(vinyla- mine), alkylenepolyamine, or polyallylamine or poly(C2-6-alkyleneimine), for example, in one embodiment, polyethyleneimine.
  • the polyamine or polyalkyleneimine may be linear or branched.
  • the polyamine or polyalkyleneimine may have a number average molecular weight of from 140-100, OOOg/mole; more desirably from 140 to 75,000; or preferably from 200 to 10,000 or 20,000.
  • X may have a total of at least four primary and/or secondary amine groups per molecule and more desirably at least six primary and/or secondary amine groups.
  • Linear polyethyleneimine may be prepared by the hydrolysis of poly(N- acyl) alkyleneimines as described, for example, by Takeo Saegusa et al in Macromolecules, 1972, Vol 5, page 4470.
  • Polypropyleneimine dendrimers are commercially available from DSM Fine Chemicals and poly(amidoamine) dendrimers are available as “Starburst” dendrimers from Aldrich Chemical Company.
  • Alkylenepolyamines may be characterized as having less than two, usually less than 1% (by weight) material boiling below about 200°C and include still bottoms such as ethylene polyamine still bottoms obtained from the Dow Chemical Company of Freeport, Texas [0031]
  • X is a polyimine, in one exemplary embodiment, it is poly (C2-6- alkyleneimine) or polyethyleneimine (PEI).
  • the polyimine may be linear or especially branched.
  • X comprises or consists of an amine.
  • X may comprise a mixture of an amine and an alkali metal or an alkaline earth metal, or a mixture of such metals.
  • the metal may be present in amounts of up to 50% by weight, or in some embodiments, no more than 50% by weight of X, or even no more than 40%, or 30%, or 25%, or 20%, or 10%, or 5% by weight.
  • both P and X may have multiple co-reactive groups, in some cases, there may be more than one bond (as defined above) between them. It is also acknowledged that more than one P can be bonded to a single X. Similarly, there can 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.
  • polymer intermediate P and species X are reacted together such that -CO2H or -CCh' of P reacts with the amine, metal, or other basic groups of X to give ionic salt bonds and/or covalent bonds or a mixture of ionic salt bonds and covalent bonds.
  • the weight ratio of P to X 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.
  • the reaction product or co-polymer product of P and X may be presented as a neat polymer or a polymer in an organic solvent. This can be achieved by dissolving the neat reaction product or co-polymer product into the solvent, or by carrying out the synthesis of the reaction product or co-polymer product in the solvent.
  • the solvent comprises or consists of ethylene glycol, oligomers of ethylene glycol, or mixtures thereof.
  • the dispersion used in the present invention also includes one or more pigments or other particulate solid material.
  • the solid is an organic pigment from any of the recognised classes of pigments described, for example, in the Third Edition of the Colour Index (1971) and subsequent revisions of, and supplements thereto, under the chapter headed “Pigments”.
  • organic pigments are those from the azo, disazo, trisazo, condensed azo, azo lakes, naphthol pigments, anthanthrone, anthrapyrimidine, anthraquinone, benzimidazolone, carbazole, diketopyrrolopyrrole, flavanthrone, indigoid pigments, indanthrone, isodibenzanthrone, isoindanthrone, isoindolinone, isoindoline, isoviolanthrone, metal complex pigments, oxazine, perylene, perinone, pyranthrone, pyrazoloquinazolone, quin- acridone, quinophthalone, thioindigo, triarylcarbonium pigments, triphendioxazine, xanthene and phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, and also lakes of acid, basic and mor
  • the organic pigments are phthalocyanines, especially copper phthalocyanines, monoazos, disazos, indanthrones, anthranthrones, quinacridones, diketopyrrolopyrroles, perylenes and carbon blacks.
  • inorganic pigments include metallic oxides such as titanium dioxide, rutile titanium dioxide and surface coated titanium dioxide, titanium oxides of different colours such as yellow and black, iron oxides of different colours such as yellow, red, brown and black, zinc oxide, zirconium oxides, aluminium oxide, oxy-metallic 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 aluminium, Prussian blue, vermillion, ultramarine, zinc phosphate, zinc sulphide, molybdates and chromates of calcium and zinc, metal effect pigments such as aluminium flake, copper, and copper/zinc alloy, pearlescent flake such as lead carbonate and bismuth oxychloride.
  • metallic oxides such as titanium dioxide, rutile titanium dioxide and surface coated titanium dioxide, titanium oxides of different colours such as yellow and
  • Inorganic solids include extenders and fillers such as ground and precipitated calcium carbonate, calcium sulphate, calcium oxide, calcium oxalate, calcium phosphate, calcium phosphonate, barium sulphate, barium carbonate, magnesium oxide, magnesium hydroxide, natural magnesium hydroxide or brucite, precipitated magnesium hydroxide, magnesium carbonate, dolomite, aluminium trihydroxide, aluminium hydroperoxide or boehmite, calcium and magnesium silicates, aluminosilicates including nanoclays, kaolin, montmorillonites including bentonites, hectorites and saponites, mica, talc including muscovites, phlogopites, lepidolites and chlorites, chalk, synthetic and precipitated silica, fumed silica, metal fibres and powders, zinc, aluminium, glass fibres, refractory fibres, carbon black including single- and multi-walled carbon nanotubes, reinforcing and non-reinforcing carbon black,
  • Other useful solid materials include flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine, melamine cyanurate, antimony oxide and borates.
  • flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclododecane, ammonium polyphosphate, melamine, melamine cyanurate, antimony oxide and borates.
  • the pigment comprises or consists of carbon black.
  • the dispersion of the present invention may be prepared by methods known and understood by those skilled in the art.
  • the dispersion used in the methods of the present invention comprises 0.5% to 40% by weight pigment, 0.5% to 40% by weight of the dispersant described herein, and 20% to 99% by weight solvent. Small amounts of other additives may be included in the dispersion as described herein and understood to those skilled in the art.
  • the solvent is primarily or solely ethylene glycol.
  • the solvent is primarily or solely oligomers of ethylene glycol having 2 to 5 repeat units of ethylene glycol.
  • the dispersant used in the methods 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% solution of the dispersant in ethylene glycol.
  • the method of the present invention further includes the steps of adding to the dispersion a material having a boiling point higher than temperature (T), which is the boiling point of the solvent.
  • T temperature
  • the solvent comprises or consists of ethylene glycol or oligomers of ethylene glycol having 2 to 5 repeat units.
  • temperature T may be at least 180 °C, or 190 °C, or 195 °C, or even at least 200 °C.
  • Materials which have a boiling point higher than temperature T may include other solvents but may also include reactive monomeric components.
  • the materials having a boiling point higher than temperature (T) include monomers formed by the reaction product of a lower-aliphatic glycol with dimethyl terephthalate or the reaction product of a lower-aliphatic diol with terephthalic acid.
  • the materials having a boiling point higher than temperature (T) may also include bis(2-hydroxyethyl)terephthalate, 2- hydroxy ethyl terephthalic acid, or mixtures thereof.
  • the mixture After mixing or while mixing the material having a boiling temperature higher than (T) with the dispersion described herein the mixture is heated to a temperature that is 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, for example, 200 °C to 300 °C, or even 250 °C to 295 °C.
  • the dispersant of the present invention unexpectedly provides a stable pigment dispersion at elevated temperatures.
  • the present invention also provides a method for producing a pigmented polymer comprising the steps 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 the reaction of (i) a maleic anhydride containing polymer, (ii) polyether mono-nucleophile C, and, optionally, (iii) a non-polymeric mono-nucleophile D, and X is an alkali metal, an alkaline earth metal, ammonia, an amine or mixtures thereof.
  • the present invention also includes the use of a pigment dispersion in the manufacture of a polymer, for example, polyethylene terephthalate, wherein the pigment dispersion contains the dispersant as described herein.
  • the pigmented polymer prepared by the method of the present invention is polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • monomers for preparation of PET polymer are formed by transesterification or esterification reactions.
  • the monomers are prepared by the transesterification or esterification reaction of dimethyl terephthalate and a lower-aliphatic diol (such as ethylene glycol or mono-ethylene glycol) or terephthalic acid and a lower aliphatic diol (such as ethylene glycol or mono-ethylene glycol).
  • the products of the transesterification or esterification reactions include bis-(2-hydroxy ethyl) terephthalate or 2-hy- droxyethyl terephthalic acid.
  • the dispersion described herein and the product of the transesterification or esterification reaction are mixed and then heated to temperatures 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, for example, 200 °C to 300 °C, or even 250 °C to 295 °C.
  • the polymer produced by the method of the present invention comprises from 0.01 to 20% based on the weight of the polymer, further for example 0.1 to 2% by weight, or even 0.4% to 1.6% by weight of the pigment.
  • the pigment comprises carbon black.
  • Comparative example 1 Orotan SN (Dow) - Naphthalene sulfonic acid-formaldehyde condensate.
  • Comparative example 2 Morwet D-809 (Nouryon) Naphthalene sulfonic acid-formaldehyde condensate
  • the mill base (1.00 g) was then removed from the vial and charged to a 32 mL vial.
  • Ethylene glycol (6.75 g) was charged to the vial, and the contents was then stirred until homogeneous to produce a dilute mill base.
  • the vial was heated to 200 °C. Once the dilute mill base had reached 200 °C it was examined to determine if it was homogeneous or not. With non-homogeneous materials having a much greater proportion of pigment at the bottom of the vial and with homogeneous being a pass.
  • Table 1 The results are summarized in Table 1.
  • Test 2 Addition of Material Having a Boiling Point Higher than Ethylene Glycol solvent (Bis-(2-hydroxyethyl) terephthalate (“BHET”)) at 200 °C: The material resulting from Test 1 was carried forward into Test 2. BHET (7.75 g) was charged to the vial at 200 °C. Once the BHET had melted the sample was stirred and heated for a further hour. This process was repeated a further two times, so that in total 23.25 g of BHET had been added in total and the sample had been heated for a total of 3 hours. The sample is allowed to cool to room temperature.
  • BHET Bis-(2-hydroxyethyl) terephthalate
  • the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open- ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative narrower embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé de production d'un polymère à l'aide d'une dispersion de pigment qui est stable à températures élevées, la dispersion contenant un pigment, un solvant et un dispersant qui est un sel d'un polyacide à fonction polyéther.
PCT/US2021/061932 2020-12-18 2021-12-06 Procédé de production d'un polymère à l'aide d'une dispersion de pigment WO2022132470A1 (fr)

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CN202180084908.3A CN116568724A (zh) 2020-12-18 2021-12-06 使用颜料分散体来制备聚合物的方法

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PCT/US2021/062133 WO2022132492A1 (fr) 2020-12-18 2021-12-07 Procédé de production d'un polymère à l'aide d'une dispersion de pigment

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830773A (en) * 1971-12-29 1974-08-20 Eastman Kodak Co Polyester film base having uniform high optical density
US4603073A (en) * 1983-12-22 1986-07-29 Minnesota Mining And Manufacturing Company Opaque polyester film containing fine carbon black particles
US20030105214A1 (en) 2001-11-30 2003-06-05 Uwe Bayer Thermally stable polyester, process for its preparation and its use
US20100022662A1 (en) * 2006-12-27 2010-01-28 Goebelt Bernd Modified comb copolymers
WO2011139580A2 (fr) * 2010-04-26 2011-11-10 Lubrizol Advanced Materials, Inc. Composition de dispersant

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ187714A (en) 1977-07-15 1980-09-12 Ici Ltd Dispersing agent reaction product of a polyalkylene imine and a polyester
DE3582887D1 (de) 1985-01-22 1991-06-20 Ici Plc Dispergiermittel enthaltende zusammensetzung.
US4733005A (en) 1986-04-21 1988-03-22 The Dow Chemical Company Phosphinyl-containing ethylenically unsaturated compounds
DE68919600T2 (de) 1988-08-26 1995-05-11 Nippon Oils & Fats Co Ltd Pigmentdispergiermittel.
US5151218A (en) 1989-09-14 1992-09-29 Byk-Chemie Gmbh Phosphoric acid esters, method of producing them, and use thereof as dispersants
DE3930687A1 (de) 1989-09-14 1991-04-11 Byk Chemie Gmbh Phosphorsaeureester, verfahren zu deren herstellung und deren verwendung als dispergiermittel
GB9306222D0 (en) 1993-03-25 1993-05-19 Zeneca Ltd Dispersants
US6194539B1 (en) 1994-11-22 2001-02-27 Daicel Chemical Industries, Inc. Polylactone having amino groups, a process for the preparation thereof, a compound having amino group, a composition for coatings, a composition for printing inks
JP3718915B2 (ja) 1995-10-16 2005-11-24 味の素株式会社 顔料分散剤
JP3488001B2 (ja) 1995-12-08 2004-01-19 ダイセル化学工業株式会社 顔料分散剤、塗料組成物及び印刷インキ組成物
GB9622783D0 (en) 1996-11-01 1997-01-08 Zeneca Ltd Dispersants
DE19732251B4 (de) 1997-07-26 2004-07-29 Byk-Chemie Gmbh Versalzungsprodukte von Polyaminen und deren Einsatz als Dispergiermittel für Pigmente und Füllstoffe
DE19750618A1 (de) 1997-11-14 1999-05-20 Basf Ag Pigmenthaltige Zubereitungen auf der Basis wässriger Polymerisatdispersionen
ES2187083T3 (es) 1998-02-19 2003-05-16 Goldschmidt Ag Th Esteres de acido fosforico y su utilizacion como agentes dispersantes.
US6878799B2 (en) 2001-03-12 2005-04-12 King Industries, Inc. Acid functional polymer dispersants
JP4248207B2 (ja) 2002-08-29 2009-04-02 川研ファインケミカル株式会社 分散剤
US7043623B2 (en) 2003-01-22 2006-05-09 Intelitrac, Inc. Distributed memory computing environment and implementation thereof
KR101067082B1 (ko) 2003-07-18 2011-09-22 더루브리졸코오퍼레이션 조성물
ATE448236T1 (de) 2004-03-08 2009-11-15 Basf Se Phosphorsäureester und deren verwendung als netz- und dispersionsmittel
JP4031471B2 (ja) 2004-07-30 2008-01-09 モレックス インコーポレーテッド Ｆｐｃ用コネクタ
US7671119B2 (en) 2004-12-21 2010-03-02 Lubrizol Limited Compositions
DE602005014672D1 (de) 2004-12-21 2009-07-09 Lubrizol Ltd Zusammensetzungen
DE102005004024A1 (de) 2005-01-28 2006-08-03 Goldschmidt Gmbh Polyether/Polyester enthaltende Dispergierharze
KR101334798B1 (ko) 2005-04-13 2013-11-29 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 분산제
EP1879689B1 (fr) 2005-05-12 2014-07-09 Lubrizol Limited Dispersants et compositions les contenant
WO2007039605A1 (fr) 2005-10-04 2007-04-12 Akzo Nobel Coatings International B.V. Résine dispersante de polyamine amphiphile
EP1957189B1 (fr) 2005-12-06 2011-10-19 Lubrizol Limited Nouveau dispersant et ses compositions
EP2126020B1 (fr) 2006-12-22 2011-11-23 Basf Se Polyalkylèneimines modifiées hydrophobiquement comme inhibiteurs du transfert de couleurs
JP4866255B2 (ja) 2007-01-30 2012-02-01 大日精化工業株式会社 カラーフィルター用着色組成物
US7923474B2 (en) 2007-02-27 2011-04-12 Ppg Industries Ohio, Inc. Amine dispersants, organic dispersions and related coating compositions
US8010601B2 (en) 2007-12-21 2011-08-30 Waldeck Technology, Llc Contiguous location-based user networks
JP5408476B2 (ja) 2009-03-25 2014-02-05 Ｄｉｃ株式会社 顔料分散剤及び顔料分散体
WO2012008619A1 (fr) 2010-07-15 2012-01-19 味の素株式会社 Polyamine modifiée
ES2591007T3 (es) 2011-03-14 2016-11-24 Lubrizol Advanced Materials, Inc. Polímero y composiciones del mismo
WO2013063209A2 (fr) * 2011-10-26 2013-05-02 Lubrizol Advanced Materials, Inc. Composition de dispersant
US9157361B2 (en) 2012-06-08 2015-10-13 GM Global Technology Operations LLC Pivoting fluid fill port for a fluid system of a vehicle
US9157374B2 (en) 2012-08-31 2015-10-13 Hamilton Sundstrand Corporation Antirotated piston rack
TWI643884B (zh) * 2013-09-06 2018-12-11 盧伯利索先進材料有限公司 多元酸多元鹼接枝共聚物分散劑

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830773A (en) * 1971-12-29 1974-08-20 Eastman Kodak Co Polyester film base having uniform high optical density
US4603073A (en) * 1983-12-22 1986-07-29 Minnesota Mining And Manufacturing Company Opaque polyester film containing fine carbon black particles
US20030105214A1 (en) 2001-11-30 2003-06-05 Uwe Bayer Thermally stable polyester, process for its preparation and its use
US20100022662A1 (en) * 2006-12-27 2010-01-28 Goebelt Bernd Modified comb copolymers
WO2011139580A2 (fr) * 2010-04-26 2011-11-10 Lubrizol Advanced Materials, Inc. Composition de dispersant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAKEO SAEGUSA ET AL., MACROMOLECULES, vol. 5, 1972, pages 4470

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WO2022132492A1 (fr) 2022-06-23
TW202239782A (zh) 2022-10-16
CN116568731A (zh) 2023-08-08
CN116568724A (zh) 2023-08-08

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