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WO2009009554A1 - Colorant azo - Google Patents

Colorant azo Download PDF

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Publication number
WO2009009554A1
WO2009009554A1 PCT/US2008/069460 US2008069460W WO2009009554A1 WO 2009009554 A1 WO2009009554 A1 WO 2009009554A1 US 2008069460 W US2008069460 W US 2008069460W WO 2009009554 A1 WO2009009554 A1 WO 2009009554A1
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WIPO (PCT)
Prior art keywords
optionally substituted
alkyl
azo
group
polyoxyalkylene
Prior art date
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PCT/US2008/069460
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English (en)
Inventor
Howard P. Klein
Keith Moody
Ai Ying Ng
Lida Joubran
Christopher Healy
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Indorama Ventures Oxides Australia Pty Ltd
Original Assignee
Huntsman Corp Australia Pty Ltd
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Publication of WO2009009554A1 publication Critical patent/WO2009009554A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes

Definitions

  • the present invention relates to an azo colourant, an azo pigment composition comprising the azo colourant, a method of preparing the colourant, a method of preparing an azo pigment, an intermediate compound used in preparing the colourant, and to a method of preparing the intermediate compound.
  • Azo colourants are compounds comprising one or more chromophoric groups and have long been used to colour a diverse array of substances. Azo colourants include both azo dyes and azo pigments.
  • the ability to efficiently disperse an azo pigment in a given liquid medium is very important for the process of colouring.
  • the efficient dispersion of an azo pigment in a liquid medium leads to optimum usage of that pigment to provide for example improved surface properties such as gloss and colour strength.
  • an azo pigment concentrate may be prepared by combining the pigment with a dispersant which, along with shear forces applied during mixing, assists in the formation of a good dispersion and provides stability of the dispersion on standing.
  • a dispersant typically minimise or prevent flocculation of the pigment on standing through steric or electrostatic means.
  • Pigment manufacturers are also known to add surface coatings to azo pigments which assist with their dispersion.
  • the present invention therefore provides an azo colourant which is a product derived from a diazotized form of an arylamine of general formula (I):
  • X is a polyoxyalkylene
  • m is an integer ranging from 1 to 10 and when m>l each [A-X]- can be the same or different
  • Y is selected from hydrogen, A, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy
  • Ar is an optionally substituted aryl group
  • R 1 is selected from hydrogen, optionally substituted alkyl, and optionally substituted aryl.
  • an arylamine of general formula (I) may be used efficiently and effectively in the preparation of a novel class of azo colourants.
  • the diazotized form of the arylamine of formula (I) can advantageously function as a key building block in the preparation of a diverse array of azo colourants, and in doing so uniquely locates the carboxamide linked polyoxyalkylene substituent on the aryl diazonium residue of the colourant.
  • the arylamine of formula (I) itself can advantageously be prepared by an effective and efficient synthetic pathway using relatively inexpensive reagents.
  • the solubility of the azo colourant in a given liquid medium can advantageously be tailored.
  • the presence of this azo colourant in azo pigment compositions has been found to improve the dispersability of the pigment in a liquid medium.
  • the present invention therefore also provides an azo pigment composition
  • an azo colourant which is a product derived from a diazotized form of the arylamine of general formula (I):
  • X is a polyoxyalkylene
  • m is an integer ranging from 1 to 10 and when m>l each [A-X]- can be the same or different
  • Y is selected from hydrogen, A, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy
  • Ar is an optionally substituted aryl group
  • R 1 is selected from hydrogen, optionally substituted alkyl, and optionally substituted aryl.
  • the present invention further provides a method of preparing an azo colourant which comprises a step of forming a diazonium intermediate from an arylamine, wherein the arylamine is a polyoxyalkylene substituted arylamine of general formula (I):
  • X is a polyoxyalkylene
  • m is an integer ranging from 1 to 10 and when m>l each [A-X]- can be the same or different
  • Y is selected from hydrogen, A, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy
  • Ar is an optionally substituted aryl group
  • R 1 is selected from hydrogen, optionally substituted alkyl and optionally substituted aryl.
  • the present invention also provides a method of preparing an azo pigment composition which comprises a step of forming a diazonium intermediate from an arylamine, wherein the arylamine comprises a polyoxyalkylene substituted arylamine of general formula (I):
  • X is a polyoxyalkylene
  • m is an integer ranging from 1 to 10 and when m>l each [A-X]- can be the same or different
  • Y is selected from hydrogen, A, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy
  • Ar is an optionally substituted aryl group
  • R 1 is selected from hydrogen, optionally substituted alkyl and optionally substituted aryl.
  • the present invention further provides a polyoxyalkylene substituted arylamine of general formula (I):
  • A is H 2 N
  • Ar C- -N— X is a polyoxyalkylene
  • m is an integer ranging from 1 to 10 and when m>l each [A-X]- can be the same or different
  • Y is selected from hydrogen, A, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy
  • Ar is an optionally substituted aryl group
  • R is selected from hydrogen, optionally substituted alkyl and optionally substituted aryl.
  • Q is hydrogen or methyl and w is an integer ranging from 4 to 200.
  • the present invention also provides a method of preparing a polyoxyalkylene substituted arylamine, the process comprising coupling an arylamine of general formula (II) with a compound comprising a polyoxyalkylene amine:
  • the present invention further provides a method of preparing a polyoxyalkylene substituted arylamine, the process comprising catalytic hydrogenation of a nitro group in a compound of general formula (III):
  • X is a polyoxyalkylene
  • m is an integer ranging from 1 to 10 and when m>l each [A-X]- can be the same or different
  • Y is selected from hydrogen, A', optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy
  • Ar is an optionally substituted aryl group
  • R 1 is selected from hydrogen, optionally substituted alkyl and optionally substituted aryl.
  • azo colourant used herein has a well known and understood meaning within the art.
  • azo colourant is intended to embrace both azo dyes and azo pigments.
  • a colourant may be described as a dye when it is substantially soluble in a given liquid medium, and described as a pigment when it is substantially insoluble in a given liquid medium.
  • an azo dye will be substantially soluble in a given liquid medium, whereas an azo pigment will be substantially insoluble in a given liquid medium.
  • An azo dye may present as a solid or liquid, whereas an azo pigment will typically be a solid.
  • an azo dye may be formed into an azo pigment by precipitating the dye from solution through formation of an insoluble metal salt. A pigment formed in this manner is often described as a "lake pigment”.
  • variation of the nature (e.g. molecular composition and/or chain length) of the polyoxyalkylene substituent of an azo colourant in accordance with the invention can advantageously alter its solubility in a given liquid medium.
  • variation of the nature (e.g. molecular composition and/or chain length) of the polyoxyalkylene substituent of an azo colourant in accordance with the invention can advantageously alter its solubility in a given liquid medium.
  • the azo colourant has been used herein rather than the terms "azo dye” or "azo pigment”.
  • the modified solubility characteristics afforded by an azo colourant in accordance with the invention can potentiate or facilitate the dispersion of an azo pigment in a given liquid medium.
  • the dispersability of an azo pigment in a given liquid medium can be improved by providing the azo pigment in admixture with an azo colourant in accordance with the invention (which will generally have a higher solubility in the liquid medium relative to the azo pigment).
  • improved dispersability is meant that the improvement is relative to the dispersability of the azo pigment in the liquid medium absent the azo colourant in accordance with the invention.
  • the azo colourant When the azo colourant is used in combination with an azo pigment to improve the pigments dispersability, it is not entirely clear how the azo colourant gives rise to this effect. However, without wishing to be limited by theory, it is believed that the azo colourant may absorb onto the surface of the azo pigment and in effect modify the solubility characteristics of the pigment such that its dispersability in the liquid medium is improved.
  • an azo pigment composition in accordance with the invention may advantageously function as a self-dispersing azo pigment composition.
  • the composition can be readily and efficiently dispersed in a given liquid medium without the assistance of conventional dispersing agents.
  • the pigment composition can also advantageously provide improved gloss and/or colour strength.
  • the azo colourant may also improve other properties of a pigment composition.
  • the polyoxyalkylene substituent(s) of the azo colourant may also serve to minimise or prevent flocculation (i.e. through steric repulsive forces) of the pigment upon its dispersion within the liquid medium.
  • the polyoxyalkylene substituent(s) might also function to improve the rheological properties of the azo pigment composition.
  • the polyoxyalkylene substituent(s) may function to reduce the viscosity of the pigment composition (i.e. make it more flowable). It will be appreciated that such improved properties of the azo pigment composition are also relative to the azo pigment composition in the absence of the azo colourant in accordance with the invention.
  • azo pigments may be used in applications that require the pigment to be dispersed in either hydrophilic or hydrophobic liquid media, which in practice may correspond to aqueous or non-aqueous liquid media, respectively.
  • the medium in which the pigment is to be dispersed may be liquid at room temperature or may require heat to cause it to become liquid.
  • the liquid medium may be molten thermoplastic polymer.
  • the amount of azo colourant required to improve the dispersability of an azo pigment composition in accordance with the invention will vary depending on several factors such as the nature of the liquid medium in which the composition is to be dispersed, the nature of the pigment that is to be dispersed, and the nature of the polyoxyalkylene substituent of the colourant.
  • the pigment composition in accordance with the invention will generally comprise up to about 20 wt.% of the colourant, preferably about 2 to about 15 wt.% of the colourant, more preferably from about 5 to about 10 wt.% of the colourant, relative to the total mass of the azo pigment(s) to be dispersed.
  • the azo colourants in accordance with the invention will in their own right be capable of functioning as a dye or pigment per se.
  • the pigment compositions of the invention may therefore also comprise from 1 to 99 wt. % of the azo colourant.
  • An azo pigment composition in accordance with the invention may be prepared by any suitable means.
  • the colourant may be physically combined and mixed with a desired azo pigment(s).
  • the azo colourant may be synthetically prepared as part of the synthetic procedure used to prepare the azo pigment. Further details of this later approach are discussed below.
  • azo pigment there is no particular limitation on the type of azo pigment that may be used in accordance with the invention.
  • suitable azo pigments include, but are not limited to, Pigment Red 57, azo-acetoacetanilides such as monoarylides and diarylides, and Naphthol Red.
  • azo colourant there is no particular limitation on the type of azo colourant that may be combined with an azo pigment so as to improve it's dispersability.
  • the azo colourant may be desirable for the azo colourant to have a similar molecular structure to the azo pigment with which it is to be combined, hi this case, the azo colourant will generally have a similar if not the same colour as the azo pigment, thereby minimising or avoiding any colour shift the colourant may impart to the pigment.
  • an azo pigment such as Pigment Red 57 having a molecular structure of formula (a) below may form an azo pigment composition in accordance with the invention by being in admixture with an azo colourant having general molecular structure (b) below (see Scheme 1).
  • the azo colourant is a product derived from a diazotized form of an arylaniine of general formula (I).
  • the process by which azo colourants are formed is well known in the art and typically comprises (a) the diazotization of a primary arylamine, and (b) coupling of the resulting diazonium salt with a "coupling compound” (i.e. a compound having a sufficiently activated hydrogen atom to participate in the azo coupling reaction, the likes of which are well known to those skilled in the art).
  • a "coupling compound” i.e. a compound having a sufficiently activated hydrogen atom to participate in the azo coupling reaction, the likes of which are well known to those skilled in the art.
  • a diazotized form of 4-aminotoluene-3-sulfonic acid with the coupling compound 3-hydroxy-2-naphthoic acid.
  • the present invention is in part based on the recognition that a diazotized form of the arylamine of formula (I) can advantageously function as a key building block in the preparation of a diverse array of azo colourants.
  • a diazotized form of an arylamine of general formula (I) is a reference to the diazonium derivative of the arylamine (i.e. where the -NH 2 moiety in formula (I) is converted to a -N 2 + moiety) and in effect identifies where within the molecular structure of the azo colourant product the polyoxyalkylene moiety resides.
  • the polyoxyalkylene moiety (X) resides on the residue of the diazotized arylamine and not on the hydroxy naphthoic acid moiety (which in this case is the coupling compound).
  • This general principle may be conveniently applied to ascertain where the polyoxyalkylene moiety (X) resides in the molecular structure of all azo colourants in accordance with the invention.
  • An azo colourant in accordance with the invention may therefore also conveniently be represented by general formula (IV):
  • X, Ar and R 1 are as herein defined; m is an integer ranging from 1 to 10 and when m>l each [B-X]- can be the same or different; Y is selected from hydrogen, B, optionally substituted alkyl, optionally substituted aryl, optionally substituted arylalkyl optionally substituted alkyleneoxy and optionally substituted aryloxy; and Z is an organic substituent that provides the colourant with desired chromophoric properties.
  • Z in general formula (IV) being defined as "an organic substituent that provides the colourant with desired chromophoric properties" is meant that Z is in effect an organic substituent that represents the remaining portion of the azo colourant.
  • Z will typically represent the reaction residue of coupling compound which through reaction with the diazotized arylamine of general formula (I) forms the desired azo colourant.
  • Z in general formula (IV) will generally be selected from optionally substituted aryl and optionally substituted alkyl.
  • Preferred optionally substituted aryl groups of Z include, but are not limited to, optionally substituted phenyl, optionally substituted biphenyl, optionally substituted terphenyl, and optionally substituted naphthyl.
  • a preferred optionally substituted alkyl group for Z includes, but is not limited to, -CHR x R y where R x is optionally substituted acyl and R y is optionally substituted amido.
  • each R 3 is independently selected from hydrogen, optionally substituted C 1-6 alkyl, optionally substituted C 6-18 aryl, optionally substituted C 6-24 arylalkyl, optionally substituted Ci -6 alkoxy, halogen, amino, and nitro.
  • X represents a polyoxyalkylene
  • polyoxyalkylene is well known to those skilled in the art and as used herein is intended to take its conventional meaning (i.e. an oligomer or polymer built up from oxyalkylene units).
  • the polyoxyalkylene may be branched or linear.
  • the polyoxyalkylene will generally have a number average molecular weight of about
  • the polyoxyalkylene substituent will generally comprise about 3 to about 200, preferably from about 10 to about 100, more preferably from about 20 to about 60 oxyalkylene units.
  • oxyalkylene used herein is intended to mean a divalent -0(CR 4 R 5 ),- group, where R 4 and R 5 are each independently selected from hydrogen and optionally substituted alkyl; and i is an integer ranging from 1 to 10.
  • R 4 and R 5 are each independently selected from hydrogen and optionally substituted C 1-6 alkyl.
  • i is an integer selected from 2, 3, and 4.
  • i > 1 each (CR 4 R 5 ) may be the same or different.
  • Each oxyalkylene group or unit within the polyoxyalkylene may be the same or different.
  • the polyoxyalkylene may be a homopolymer or a copolymer (including a random or block copolymer).
  • Preferred oxyalkylene units of X are derived from an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide.
  • m is an integer ranging from 1 to 10.
  • m is an integer ranging from 1 to 6, more preferably m is an integer selected from 1, 2 and 3.
  • each [A-X]-, [A'-X]-, or [B-X]- can be the same or different.
  • each [A-X]-, [A'-X]-, or [B-X]- represent a repeat unit of an oligomeric or polymeric structure.
  • each [A-X]-, [A'-X]-, or [B-X]- is intended to represent a moiety connected to the group Y (e.g. see formula (Ia) below).
  • Y is preferably selected from, hydrogen, A (or A' or B), optionally substituted Ci -9 alkyl, optionally substituted C 6-18 aryl, optionally substituted C 6-24 arylalkyl, optionally substituted C 2-9 alkyleneoxy, and optionally substituted C 6-18 aryloxy.
  • alkylenoxy moieties include, but are not limited to, 1,2-ethylenedioxy and 1,2,3-propylenetrioxy.
  • aryloxy moieties include, but are not limited to, 1 ,4-phenyldioxy and 1,3,5-phenyltrioxy.
  • the polyoxyalkylene moiety X may terminate with a -OH moiety. Having the polyoxyalkylene moiety terminate in a -OH moiety may be desirable to provide a reactive site whereby the azo colourant in accordance with the invention can react with a component of the medium within which it is to be dispersed. For example, it may be desirable to have the colourant react with the polymeric matrix of the polymer within which it is to be dispersed. Reaction of the colourant in this way can be used to prevent migration of the colourant upon being dispersed in a polymer.
  • Y can form together with X other reactive end groups to achieve a similar effect.
  • Ar is an optionally substituted aryl group.
  • Ar is preferably selected from optionally substituted phenyl, optionally substituted biphenyl, optionally substituted terphenyl, and optionally substituted naphthyl.
  • Preferred optional substituents for Ar include, but are not limited to, alkyl (preferably C 1 . 6 alkyl), aryl (preferably C 6-I8 aryl), alkoxy (preferably Ci -6 alkoxy), halogen, nitro, amino (preferably -NH 2 ),
  • R . 1 , r R>3 , X and Y are as herein defined.
  • preferred optional substituents for Ar might also include, but are not limited to,
  • arylamine or general formula (I) comprises an Ar group having more than one primary amine substituent
  • the diazotized form of the arylamine may comprise more than one diazonium moiety.
  • an arylamine falling within the scope of general formula (I) may be represented by general formula (Ib):
  • each primary arylamine moiety of general formula (Ib) may be diazotized and the resulting compound coupled with an appropriate coupling compound(s) to form the azo colourant.
  • an azo colourant which is a product derived from a diazotized form of an arylamine of general formula (Ib) might be conveniently represent by general formula (Ic):
  • R 1 , X, Y and Z are as herein defined.
  • R 1 is preferably selected from hydrogen, optionally substituted C 1-6 alkyl and optionally substituted C 6-I8 aryl. More preferably, R is hydrogen.
  • alkyl used either alone or in compound words denotes straight chain, branched or cyclic alkyl, preferably C 1-20 alkyl, e.g. Ci -10 or Ci -6 .
  • straight chain and branched alkyl include methyl, ethyl, ⁇ -propyl, isopropyl, r ⁇ -butyl, sec-butyl, t-butyl, r ⁇ -pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4- methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2- dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2- trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl
  • cyclic alkyl examples include mono- or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is referred to generally as "propyl", butyl” etc, it will be understood that this can refer to any of straight, branched and cyclic isomers where appropriate. An alkyl group may be optionally substituted by one or more optional substituents as herein defined.
  • alkenyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon to carbon double bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined, preferably C 2-20 alkenyl (e.g. C 2-I0 or C 2-6 ).
  • alkenyl examples include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3- decenyl, 1,3-butadienyl, 1 ,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4- hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5- cyclo
  • alkynyl denotes groups formed from straight chain, branched or cyclic hydrocarbon residues containing at least one carbon-carbon triple bond including ethylenically mono-, di- or polyunsaturated alkyl or cycloalkyl groups as previously defined. Unless the number of carbon atoms is specified the term preferably refers to C 2-20 alkynyl (e.g. C 2-10 or C 2-6 ). Examples include ethynyl, 1-propynyl, 2- propynyl, and butynyl isomers, and pentynyl isomers. An alkynyl group may be optionally substituted by one or more optional substituents as herein defined.
  • halogen denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.
  • aryl denotes any of single, polynuclear, conjugated and fused residues of aromatic hydrocarbon ring systems.
  • aryl include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, idenyl, azulenyl, chrysenyl.
  • Preferred aryl include phenyl, biphenyl and naphthyl.
  • An aryl group may be optionally substituted by one or more optional substituents as herein defined.
  • carbocyclyl includes any of non-aromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3-20 (e.g. C 3-10 or C 3- 8 ).
  • the rings may be saturated, e.g. cycloalkyl, or may possess one or more double bonds (cyc ⁇ oalkenyl) and/or one or more triple bonds (cycioalkynyi).
  • Particularly preferred carbocyclyl moieties are 5-6-membered or 9-10 membered ring systems.
  • Suitable examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctatetraenyl, indanyl, decalinyl and indenyl.
  • heterocyclyl when used alone or in compound words includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, preferably C 3- 20 (e.g. C 3-I o or C 3-8 ) wherein one or more carbon atoms are replaced by a heteroatom so as to provide a non-aromatic residue.
  • Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • the heterocyclyl group may be saturated or partially unsaturated, i.e. possess one or more double bonds.
  • heterocyclyl are 5-6 and 9-10 membered heterocyclyl.
  • Suitable examples of heterocyclyl groups may include azridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpholinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazin
  • heteroaryl includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, wherein one or more carbon atoms are replaced by a heteroatom so as to provide an aromatic residue.
  • Preferred heteroaryl have 3-20 ring atoms, e.g. 3-10.
  • Particularly preferred heteroaryl are 5-6 and 9-10 membered bicyclic ring systems.
  • Suitable heteroatoms include, O, N, S, P and Se, particularly O, N and S. Where two or more carbon atoms are replaced, this may be by two or more of the same heteroatom or by different heteroatoms.
  • heteroaryl groups may include pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindo ⁇ yl, pyrazolyl, pyrazinyi, pyrimidinyl, pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinozalinyl, quinazolinyl, quinolinyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadialzolyl, oxatriazolyl, triazinyl, and furazanyl.
  • Preferred acyl includes C(O)-R, wherein R is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • R is hydrogen or an alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl residue.
  • examples of acyl include formyl, straight chain or branched alkanoyl (e.g.
  • C 1-2 o) such as, acetyl, propanoyl, butanoyl, 2- methylpropanoyl, pentanoyl, 2,2-dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and icosanoyl; cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; aroyl such as benzoyl, toluoyl and naphthoyl; a
  • phenylacetyl phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl
  • naphthylalkanoyl e.g. naphthylacetyl, naphthylpropanoyl and naphthylbutanoyl]
  • aralkenoyl such as phenylalkenoyl (e.g.
  • phenylpropenoyl e.g., phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (e.g.
  • aryloxyalkanoyl such as phenoxyacetyl and phenoxypropionyl
  • arylthiocarbamoyl such as phenylthiocarbamoyl
  • arylglyoxyloyl such as phenylglyoxyloyl and naphthylglyoxyloyl
  • arylsulfonyl such as phenylsulfonyl and napthylsulfonyl
  • heterocycliccarbonyl heterocyclicalkanoyl such as thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl
  • sulfoxide refers to a group -S(O)R wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycly ⁇ , carbocycly ⁇ , and araikyi.
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycly ⁇ , carbocycly ⁇ , and araikyi.
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycly ⁇ , carbocycly ⁇ , and araikyi.
  • R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycly ⁇ , carbocycly ⁇ , and araikyi.
  • R include C 1- 2 oalkyl, phenyl and benzyl.
  • sulfonyl refers to a group S(O) 2 -R, wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl. Examples of preferred R include C 1 . 2oalkyl, phenyl and benzyl.
  • sulfonamide refers to a group S(O) 2 NRR wherein each R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and arylalkyl.
  • R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, and arylalkyl.
  • R include Q ⁇ oalkyl, phenyl and benzyl.
  • at least one R is hydrogen.
  • both R are hydrogen.
  • amino is used here in its broadest sense as understood in the art and includes groups of the formula NR A R B wherein R A and R B may be any independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • R A and R B together with the nitrogen to which they are attached, may also form a monocyclic, or polycyclic ring system e.g. a 3- 10 membered ring, particularly, 5-6 and 9-10 membered systems.
  • Examples of "amino” include NH 2 , NHalkyl (e.g.
  • C 1-2O alkyl NHaryl (e.g. NHphenyl), NHaralkyl (e.g. NHbenzyl), NHacyl (e.g. NHC(O)C 1-20 alkyl, NHC(O)phenyl), Nalkylalkyl (wherein each alkyl, for example C 1-20 , may be the same or different) and 5 or 6 membered rings, optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • NHaryl e.g. NHphenyl
  • NHaralkyl e.g. NHbenzyl
  • NHacyl e.g. NHC(O)C 1-20 alkyl, NHC(O)phenyl
  • Nalkylalkyl wherein each alkyl, for example C 1-20 , may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e.g. O, N and
  • amido is used here in its broadest sense as understood in the art and includes groups having the formula C(0)NR A R B , wherein R A and R B are as defined as above.
  • amido include C(O)NH 2 , C(O)NHalkyl (e.g. C 1-20 alkyl), C(O)NHaryl (e.g. C(O)NHphenyl), C(O)NHaralkyl (e.g. C(O)NHbenzyl), C(O)NHacyl (e.g.
  • C(O)NHC(O)Ci -20 alkyl C(O)NHC(O)phenyl
  • C(O)Nalkylalkyl wherein each alkyl, for example C 1-20 , may be the same or different
  • 5 or 6 membered rings optionally containing one or more same or different heteroatoms (e.g. O, N and S).
  • carboxy ester 1 is used here in its broadest sense as understood in the art and includes groups having the formula CO 2 R, wherein R may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • R may be selected from groups including alkyl, alkenyl, alkynyl, aryl, carbocyclyl, heteroaryl, heterocyclyl, aralkyl, and acyl.
  • Examples of carboxy ester include C0 2 C 1-2 oalkyl, CO 2 aryl (e.g...
  • CO 2 phenyl CO 2 aralkyl (e.g. CO 2 benzyl).
  • optionally substituted is taken to mean that a group may or may not be further substituted or fused (so as to form a condensed polycyclic group) with one, two, three or more of organic and inorganic groups, including those selected from: alkyl, alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl, acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, halocarbocyclyl, haloheterocyclyl, haloheteroaryl, haloacyl, haloaryalkyl, hydroxy, hydroxyalkyl, hydroxyalken
  • Preferred optional substituents include alkyl, (e.g. C 1-6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), hydroxyalkyl (e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g. methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl etc) alkoxy (e.g..).
  • alkyl e.g. C 1-6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl
  • hydroxyalkyl e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl
  • C 1-6 alkoxy such as methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy
  • halo trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy, phenyl (which itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyCi -6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino)
  • benzyl wherein benzyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyCi -6 alkyl, C 1-6 alkoxy, haloC 1-6 alkyl, cyano, nitro OC(O)Ci -6 alkyl, and amino
  • phenoxy wherein phenyl itself may be further substituted e.g., by Ci
  • Ci -6 alkyl such as methylamino, ethylamino, propylamino etc
  • dialkylamino e.g. Cj -6 alkyl, such as dimethylamino, diethylamino, dipropylamino
  • acylamino e.g.
  • phenylamino (wherein phenyl itself may be further substituted e.g., by Ci -6 alkyl, halo, hydroxy hydroxyCi -6 alkyl, Ci -6 alkoxy, haloCi -6 alkyl, cyano, nitro OC(O)Ci -6 alkyl, and amino), nitro, formyl, -C(O)-alkyl (e.g. C 1-6 alkyl, such as acetyl), O-C(O)-alkyl (e.g.
  • C 1- 6alkyl such as acetyloxy
  • benzoyl wherein the phenyl group itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy hydroxyC 1-6 alkyl, C 1-6 alkoxy, 1IaIoC 1-6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino
  • Ci -6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl ester
  • C0 2 phenyl (wherein phenyl itself may be further substituted e.g., by C 1-6 alkyl, halo, hydroxy, hydroxyl Ci -6 alkyl, Ci -6 alkoxy, halo Ci -6 alkyl, cyano, nitro OC(O)C 1-6 alkyl, and amino), CONH 2 , CONHphenyl (wherein phenyl itself may be further substituted e.g., by Ci -6 alkyl, halo, hydroxy, hydroxyl Ci -6 alkyl, Ci -6 alkoxy, halo Ci -6 alkyl, cyano, nitro OC(O)Ci -6 alkyl, and amino), CONHbenzyl (wherein benzyl itself may be further substituted e.g., by Ci -6 alkyl, halo, hydroxy
  • Ci -6 alkyl such as methyl ester, ethyl ester, propyl ester, butyl amide) CONHdialkyl (e.g. Ci -6 alkyl) aminoalkyl (e.g., HN Ci -6 alkyl-, Ci -6 alkylHN-C 1-6 alkyl- and (C 1-6 alkyl) 2 N-C 1-6 alkyl-), thioalkyl (e.g., HS Ci -6 alkyl-), carboxyalkyl (e.g., HO 2 CCi -6 alkyl-), carboxyesteralkyl (e.g., C 1-6 alkylO 2 CCi -6 alkyl-), amidoalkyl (e.g., H 2 N(O)CCi -6 alkyl-, H(Ci -6 alkyl)N(O)CCi -6 alkyl-), formylalkyl (e.g., OHCCi -6 alkyl-),
  • heteroatom refers to any atom other than a carbon atom which may be a member of a cyclic organic group.
  • heteroatoms include nitrogen, oxygen, sulfur, phosphorous, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.
  • hydroxyethyl is intended to denote HO-CH 2 -CH-).
  • a term such as “[group A] [group B]” one or both of such subgroups may be optionally substituted.
  • methods for preparing azo colourants are well known in the art and typically comprise a step of forming a diazonium intermediate from an arylamine (i.e. a primary arylamine). It is this step in azo colourant formation with which the method of the invention is primarily concerned. Although not discussed in any detail here, additional steps in preparing azo colourants are well known to those skilled in the art.
  • the diazonium intermediate is formed from a polyoxyalkylene substituted arylamine of general formula (I).
  • the diazotized form of the arylamine of general formula (I) can advantageously function as a key building block in the preparation of a diverse array of azo colourants, and in doing so uniquely locates the carboxamide linked polyoxyalkylene substituent(s) on the aryl diazonium residue of the colourant.
  • Formation of the diazonium intermediate from the arylamine may be achieved using techniques, conditions and reagents well known in the art for converting a primary arylamine into a diazonium compound.
  • the arylamine of general formula (I) may be diazotized by reaction with hydrochloric acid/sodium nitrite.
  • the resulting diazonium intermediate may then be reacted with a suitable coupling compound again using techniques, conditions and reagents well known in the art to thereby form the azo colourant.
  • the diazo intermediate may be coupled with hydroxy naphthoic acid to form a modified Pigment Red azo colourant, or reacted with an acetoacetanilide compound to thereby form a modified mono- or di- arylide colourant.
  • the pigment compositions in accordance with the invention may be prepared by physically mixing the azo colourant with a desired azo pigment.
  • the azo colourant may be synthetically prepared as part of the synthetic procedure used to prepare the azo pigment.
  • the method in accordance with the invention for preparing an azo pigment composition comprises a step of forming a diazonium intermediate from an arylamine comprising a polyoxyalkylene substituted arylamine of general formula (I).
  • the diazonium intermediate may be formed from an arylamine of general formula (I) and one or more other arylamines.
  • the method in accordance with the invention for preparing a pigment composition might comprise forming a diazonium intermediate from a mixture of aminotoluene-3 -sulfonic acid and an arylamine of general formula (I), and then coupling the mixture of diazonium compounds with 3-hydroxy-2-naphthoic acid.
  • the resulting azo pigment composition might therefore comprise a mixture of Pigment Red 57 and an azo colourant in accordance with the invention such as that illustrated by structure (b) in Scheme 1.
  • the method of preparing a pigment composition in accordance with the invention might also comprise a step of forming a lake pigment composition. Those skilled in the art will appreciate that this will typically involve precipitating the pigment composition in the form of a metal salt such a calcium salt.
  • a method in accordance with the invention for preparing a pigment composition might comprise preparing a diarylide pigment composition using a typical reaction pathway except that a proportion of an optionally substituted benzidine is replaced with an arylamine of general formula (I) as illustrated below in Scheme 3.
  • Scheme 3 A schematic illustration of preparing a diarylide pigment composition in accordance with the method of the invention, where R 1 , X and Y are as herein defined.
  • the arylamine will generally comprise up to about 10 mol % of the arylamine of general formula (I), preferably about 1 to about 8 mol % of the arylamine of general formula (I), more preferably from about 1 to about 5 mol % of the arylamine of general formula (I), relative to the total amount of arylamine used in preparing the pigment composition.
  • the arylamine used in preparing pigment compositions in accordance with the invention may therefore also comprise from 1 to 99 mol % of the arylamine of general formula (I), relative to the total amount of arylamine used in preparing the pigment composition.
  • arylamines of general formula (I) can function as a versatile key building block in the preparation of azo colourants.
  • Certain arylamines of general formula (I) are also believed to be novel in their own right.
  • the present invention also provides polyoxyalkylene substituted arylamines of general formula (I), with the proviso that the substituted arylamine is not
  • Q is hydrogen or methyl and w is an integer ranging from 4 to 200.
  • the -NH 2 moiety in A is preferably in a meta or para position relative to the carboxamide moiety.
  • the Ar moiety in general formula (I) may also be substituted with one or more of the preferred optional substituents hereinbefore defined. It may also be desirable that Y in general formula (I) is hydrogen, or that the first oxyalkylene moiety of X connected to the carboxamide group in formula (I) is at least a C 4 oxyalkylene moiety.
  • the present invention also provides a process for preparing polyoxyalkylene substituted arylamines.
  • the process comprises coupling an arylamine of general formula (II) with a compound comprising a polyoxyalkylene amine.
  • the arylamine of general formula (II) comprises the moiety -COOR 2 , where R 2 is selected from hydrogen and a condensable organic group.
  • R 2 is selected from hydrogen and a condensable organic group.
  • a condensable organic group is meant that the -COOR 2 moiety is of a type that will undergo a condensation reaction with the amine moiety of the polyoxyalkylene compound.
  • R 2 OH
  • R 2 will generally be hydrogen or a low molecular weight alkyl group, for example a C 1-6 alkyl group, preferably a C 1-4 alkyl group.
  • Preferred Ar groups and preferred optional substituents for the Ar group in general formula (II) include those hereinbefore defined.
  • preferred optional substituents for Ar might also include, but are not limited to,
  • R 1 , R 2 , R 3 , X and Y are as herein defined.
  • an arylamine of general formula (II) comprises an Ar group having more than one -COOR 2 substituent
  • the process of preparing the polyoxyalkylene substituted arylamine in accordance with the invention might comprise coupling each -COOR 2 moiety with a compound comprising a polyoxyalkylene amine.
  • an arylamine falling within the scope of general formula (II) may be represented by general formula (Ha):
  • Each -COOR moiety of general formula (Ha) may be coupled in accordance with the invention with a compound comprising a poly oxy alky lene amine.
  • Preferred examples of compounds of general formula (II) include, but are not limited to, para- or meta- aminobenzoic acid.
  • Suitable compounds comprising a polyoxyalkylene amine may have a structure represented by general formula (V):
  • Suitable compounds comprising a polyoxyalkylene amine for use in accordance with the invention include, but are not limited to, polyoxyalkylene amines sold under the tradename JEFF AMINE ® and SURFONAMINE ® by Huntsman Corporation.
  • Suitable polyoxyalkylene amines include, but are not limited to, those structurally represented below:
  • R w , R x , R y , and R z are each independently selected from hydrogen and optionally substituted alkyl, preferably hydrogen, methyl and ethyl, q, r, and s, are each independently an integer ranging from 1 to about 80.
  • the coupling occurs through a carboxamide linkage that is formed by a condensation reaction between the -COOR 2 moiety of the arylamine (II) and the amine moiety of the polyoxyalkylene amine.
  • Condensation reactions in general are well known in the art and techniques, conditions and reagents used in such reactions can conveniently be employed in performing the condensation reaction outlined in the present invention. This method can conveniently be performed as a one step (or pot) procedure.
  • condensation reaction product i.e. typically water or a low molecular weight alcohol
  • distillation under reduced pressure or via azeotrope formation if required.
  • the condensation reaction is performed at a temperature ranging from about 15O 0 C to about 300 0 C.
  • condensation catalysts include, but are not limited to, titanate esters (for example a mixed isopropyl/n-butyl titanate ester sold under the tradename VERTEC ® BIP), tin and antimony compounds.
  • arylamine compounds of general formula (II) may, during the condensation reaction contemplated herein, be prone to self- condensation giving rise to oligo- or poly- amides.
  • the polyoxyalkylene substituted arylamines in accordance with the invention may be prepared with little if no formation of such oligo- or poly- amides. Where such self- condensation products do form, it should be possible to be remove them by passing the reaction mixture through a suitable filter.
  • the polyoxyalkylene substituted arylamines may also be prepared by a method comprising catalytic hydrogenation of a nitro group in a compound of general formula (III).
  • the -NO 2 group is converted to a -NH 2 group by catalytic hydrogenation.
  • the catalytic hydrogenation may be conducted by any suitable means. Techniques, reagents and conditions for the catalytic hydrogenation of nitro groups are well known to those skilled in the art and may be conveniently employed in the method of the present invention.
  • the catalytic hydrogenation may be performed by subjecting a compound of general formula (III) to an atmosphere of hydrogen (typically at a pressure greater than atmospheric pressure) in the presence of a suitable catalyst such as Raney nickel.
  • Preferred Ar groups and preferred optional substituents for the Ar group in general formula (III) include those hereinbefore defined.
  • preferred optional substituents for Ar might also include, but are not limited to,
  • R . 1 , ⁇ R3 , X and Y are as herein defined.
  • a compound of general formula (III) comprises an aryl group having more than one -NO 2 moiety
  • the process of preparing the polyoxyalkylene substituted arylamine in accordance with the invention might comprise catalytic hydrogenation of each -NO 2 moiety.
  • the method of forming polyoxyalkylene substituted arylamines by the catalytic hydrogenation route might also comprise a step of preparing a compound of general formula (III).
  • a compound of general formula (III) There is no particular limitation as to how compounds of general formula (III) are prepared.
  • such compounds might be prepared by coupling an aryl acid chloride of general formula (VI) with a compound comprising a polyoxyalkylene amine:
  • Coupling reactions between an acid chloride moiety and an amine moiety to form a carboxamide group are in general well known by those skilled in the art. Techniques, conditions and reagents for conducting such reactions may be conveniently used in the method of the present invention.
  • Preferred Ar groups and preferred optional substituents for the Ar group in general formula (VI) include those hereinbefore defined.
  • preferred optional substituents for Ar might also include, but are not limited to,
  • R . 1 , r R>3 , X and Y are as herein defined.
  • an aryl acid chloride of general formula (VI) comprises an Ar group having more than one -COCl moiety
  • the process of preparing the polyoxyalkylene substituted arylamine in accordance with the invention might comprise coupling each -COCl moiety with a compound comprising a polyoxyalkylene amine.
  • Preferred examples of compounds of general formula (VI) include, but are not limited to, para- or meta- nitrobenzoyl chloride.
  • Suitable compounds comprising a polyoxyalkylene amine may be represented by general formula (V) hereinbefore defined.
  • SURFONAMINE ® L200 424.8g, 0.2 moles
  • PABA p-aminobenzoic acid
  • xylene 35.Og
  • Titanate ester catalyst - VERTEC ® BIP 0.1g, 0.2% w/w of SURFONAMINE ® L200/PABA
  • SURFONAMINE ® B200 396.6g, 0.2 moles
  • PABA p-aminobenzoic acid
  • xylene 40.Og
  • Conversion by acid value was 58%.
  • Further reaction at 230°C/24hr raised conversion to 79% by acid value.
  • Further reaction at 230°C/7hr with VERTEC ® BIP(0.85g, 0.2%w/w of SURFONAMINE ® B200/PABA) resulted in 92% conversion by acid value.
  • Example 3 SURFONAMINE ® L207 (417.3g, 0.2 moles), p-aminobenzoic acid (PABA) (30.2g, 0.22 moles, 10% mole excess), VERTEC ® BIP (0.9g, 0.2%w/w of SURFONAMINE ® L207/PABA) and xylene (40.Og) were heated under reflux at 23O 0 C for 20.5hr with separation of water from the xylene/water azeotrope in a Dean & Stark side arm. After vacuum removal of xylene, a liquid product was obtained - conversion by acid value was 93%.
  • PABA p-aminobenzoic acid
  • VERTEC ® BIP 0.2%w/w of SURFONAMINE ® L207/PABA
  • xylene 40.Og
  • SURFONAMINE ® B200 396.6g, 0.2 moles
  • p-aminobenzoic acid (PABA) 27.4g, 0.2 moles
  • VERTEC ® BIP 0.85g, 0.2%w/w of SURFONAMINE ® B200/PABA
  • xylene 30.0g
  • SURFONAMINE ® BlOO 516.7g, 0.5 moles
  • PABA p-aminobenzoic acid
  • xylene 50.0g
  • titanate ester catalyst VERTEC ® BIP, 0.2%w/w of SURFONAMINE ® BIOO/PABA
  • the temperature was raised further to establish reflux, with a final reaction temperature of 230 0 C, and water of reaction was removed in a Dean & Stark side arm via a xylene/water azeotrope.
  • Example 2 The modified aniline of Example 2 (50.0g), water (20Og), ethanol (24.3g) and 36%(w/w) hydrochloric acid (5.95g) were stirred at ambient temperature for 30min, before adding ice (300g) and cooling in an ice bath. Sodium nitrite (1.6Ig) in water (7.9g) was added with stirring over a period of 5min at 0-1 0 C, and then stirred at this temperature for 3hr.
  • Sodium nitrite (1.6Ig) in water (7.9g) was added with stirring over a period of 5min at 0-1 0 C, and then stirred at this temperature for 3hr.
  • the resultant diazonium salt solution was added to a solution of 3-hydroxy-2-naphthoic acid (4.8Og), sodium carbonate (6.99g), water (15Og) and ice (10Og) at 0-2 0 C over a period of 20min, and then stirred at 2°C for 3hr.
  • the initially deep red solution set to a solid gel overnight which was filtered and pressed as dry as possible before washing with water and then drying at 100° under vacuum to give a dark red, rubbery solid (50.6g).
  • Example 3 The modified aniline of Example 3 (50.0g), water (20Og), 36%(w/w) hydrochloric acid (5.95g) and ice (12Og) were cooled in an ice bath.
  • Sodium nitrite (1.6Og) in water (7.9g) was added with stirring over a period of 6min at 0 0 C, and then the reaction mixture was stirred at 0-1 0 C for 3hr.
  • the resultant diazonium salt solution was added to a solution of 3- hydroxy-2-naphthoic acid (4.8Og), sodium carbonate (6.99g) and water (15Og) at 1-3 0 C over a period of 14min, and then stirred at 2-3 0 C for 4hr.
  • the azo product was a deep orange-red solution.
  • Example 1 The modified aniline of Example 1 (50.0g) was dissolved in 36%(w/w) hydrochloric acid
  • Example 3 The modified aniline of Example 3 (50.Og), water (200g), 36%(w/w) hydrochloric acid (5.95g) and ice (12Og) were cooled in an ice bath.
  • Sodium nitrite (2.0Og) in water (7.9g) was added with stirring over a period of 12min at 0°C, and then the reaction mixture was stirred at 0-1 0 C for 3hr.
  • the resultant diazonium salt solution was added to a solution of 3- hydroxy-2-naphthoic acid (4.37g), sodium carbonate (6.99g) and water (150g) at 1-2°C over a period of 12min, and then stirred at 0-2 0 C for 4hr.
  • the azo product was a deep orange-red solution.
  • 4-Aminotoluene-3-sulphonic acid (65.5g), the modified aniline of Example 2 (13.65g), water (105Og), ethanol (25.Og) and 36%(w/w) hydrochloric acid (91.Og) were stirred at ambient temperature for 30min, before adding ice (100Og) and cooling in an ice bath.
  • the damp filter cake was suspended in a solution of calcium chloride (59.3g) in water (3145g) and homogenized in a Silverson mixer for 3hr, warming up in the process to 50-
  • the modified Pigment Red 57 dye from Example 9 (74.5g, approx 7.5%w/w of dye) was treated with 36%w/w hydrochloric acid and pH adjusted to 4.2.
  • 4-Aminotoluene-3-sulphonic acid (65.5g), the modified aniline of Example 3 (13.65g), water (105Og), and 36%(w/w) hydrochloric acid (91.Og) were stirred at ambient temperature for 30min, before adding ice (100Og) and cooling in an ice bath.
  • the resultant diazonium salt solution was added to a coupling solution composed of 3-hydroxy-2-naphthoic acid (67.Ig), sodium hydroxide (52.Og), water (100Og) and ice (75Og) at 0-2 0 C over a period of 69min, and then stirred at 1- 2°C for a further 3hr.
  • the ice bath was removed, a solution of calcium chloride (59.3g) in water (10Og) added, and the reaction mix left stirring overnight.
  • the modified azo product (calcium salt) (162.3g) was filtered and washed well with water, before drying at 100 0 C, finally under vacuum.
  • the filtration liquors were relatively colourless indicating that the intermediate modified azo dye had been incorporated into the pigment structure.
  • 4-Aminotoluene-3-sulphonic acid (65.5g), the modified aniline of Example 1 (13.68g), water (105Og), and 36%(w/w) hydrochloric acid (91.Og) were stirred at ambient temperature for 30min, before adding ice (100Og) and cooling in an ice bath.
  • the resultant diazonium salt solution was added to a coupling solution composed of 3-hydroxy-2-naphthoic acid (67.Og), sodium hydroxide (52.Og), water (100Og) and ice (75Og) at 0-2 0 C over a period of 61min, and then stirred at 1- 2°C for a further 3hr.
  • the ice bath was removed, a solution of calcium chloride (59.3g) in water (10Og) added, and the reaction mix left stirring overnight.
  • the modified azo product (calcium salt) (162.Ig) was filtered and washed well with water, before drying at 100 0 C, finally under vacuum.
  • the filtration liquors were relatively colourless indicating that the intermediate modified azo dye had been incorporated into the pigment structure.
  • SURFONAMINE® B200 (495.8g, 0.25 moles) and triethanolamine (46Ag) were dehydrated at 130°C/0.3mmHg for 2hr and then cooled to 50 0 C.
  • 4-Nitrobenzoyl chloride (46.4g, 0.25 moles) was added gradually over a period of 5 min in which time temperature rose to 87°C. Reacted out at 8O 0 C for 3hr.
  • Triethanolamine hydrochloride by-product was filtered of and washed with dichloromethane, which was removed to give the amide product as an oil (482.8g). Amine value indicated 98.4% conversion to
  • the nitroamide product from Example 16 was converted to the corresponding aniline derivative by catalytic hydrogenation in ethanol over Raney nickel catalyst at ambient temperature and up to 50psi hydrogen pressure on a Parr medium pressure hydrogenator. After filtering catalyst, washing with ethanol and removing solvent, the aniline was obtained as an oil. Amine value, 45.6 mmoles amine/10Og. IR spectrum: amide absorption at 1636cm "1 . The Hl NMR spectrum indicated complete conversion of the nitro compound to the aniline and was consistent with the expected product.
  • Example 17 The modified aniline of Example 17 (50.Og), water (20Og), ethanol (24.3g) and 36%(w/w) hydrochloric acid (5.82g) and ice (300g) were cooled in an ice bath. Sodium nitrite (1.57g) in water (7.9g) was added with stirring over a period of 3 min at O 0 C, and then stirred at this temperature for 5hr. The resultant diazonium salt solution was added to a solution of 3- hydroxy-2-naphthoic acid (4.5Og), sodium carbonate (6.56g), water (15Og) and ice (10Og) at 2-6°C over a period of lhr, and then stirred at 4-6 0 C for 3hr. The initially deep red solution set to a solid gel overnight which was filtered and pressed as dry as possible before washing with water and then drying at 100° under vacuum to give the azo pigment as a dark red, rubbery solid (50.2g).
  • the resultant diazonium salt solution was added to a coupling solution composed of 3-hydroxy-2-naphthoic acid (73.2g), sodium carbonate (106.8g), water (154Og) and ice (50Og) at 0-3 0 C over a period of 74 min, and then stirred at 2 0 C for a further 4hr.
  • the azo product sodium salt was filtered off and dried at
  • modified azo pigment sodium salt
  • the modified azo pigment (sodium salt) (110.Og) was powdered, suspended in a solution of calcium chloride (42.6g) in water (300Og) and stirred at ambient temperature overnight, before homogenizing using a Silverson mixer for 2hr, warming up in the process to 50- 60 0 C.
  • the modified Pigment Red 57:1 was filtered off, washed well with water, dried at 100 0 C, and then at 100 0 C under vacuum.
  • Weight of modified azo product (calcium salt) was (104.8g).

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Abstract

La présente invention concerne un colorant azo et des compositions pigmentaires de celui-ci.
PCT/US2008/069460 2007-07-09 2008-07-09 Colorant azo Ceased WO2009009554A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389524A (en) * 1989-07-28 1995-02-14 Kemisk Vaerk Koge A/S Method and a system for quantitatively monitoring a chemical component dissolved in a liquid medium
US6969759B2 (en) * 2003-04-24 2005-11-29 Xerox Corporation Colorant compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389524A (en) * 1989-07-28 1995-02-14 Kemisk Vaerk Koge A/S Method and a system for quantitatively monitoring a chemical component dissolved in a liquid medium
US6969759B2 (en) * 2003-04-24 2005-11-29 Xerox Corporation Colorant compositions

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