WO2009156335A1 - Colorants azoïques pour la coloration des polyuréthannes - Google Patents

Colorants azoïques pour la coloration des polyuréthannes Download PDF

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Publication number
WO2009156335A1
WO2009156335A1 PCT/EP2009/057644 EP2009057644W WO2009156335A1 WO 2009156335 A1 WO2009156335 A1 WO 2009156335A1 EP 2009057644 W EP2009057644 W EP 2009057644W WO 2009156335 A1 WO2009156335 A1 WO 2009156335A1
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WO
WIPO (PCT)
Prior art keywords
formula
alkyl
methyl
aryl
hydrogen
Prior art date
Application number
PCT/EP2009/057644
Other languages
English (en)
Inventor
Hartwig Jordan
Andreas Runge
Werner Russ
Original Assignee
Dystar Textilfarben Gmbh & Co. Deutschland Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dystar Textilfarben Gmbh & Co. Deutschland Kg filed Critical Dystar Textilfarben Gmbh & Co. Deutschland Kg
Publication of WO2009156335A1 publication Critical patent/WO2009156335A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • 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

Definitions

  • Polyurethanes are manufactured polymers obtained by polyaddition of building blocks that contain at least two hydroxyl groups and are known as diols with building blocks that contain at least two isocyanate groups and are known as diisocyanates. Polyurethanes are generally produced as foams by generating carbon dioxide through specific inclusion of water during the polycondensation, or by adding gases from the outside.
  • Colored polyurethanes are generally produced by admixing one of the two components, namely the diol, with a dye containing at least one functional group capable of reacting with the other component, the diisocyanate, to form a covalent bond.
  • the dye is thus incorporated in the polyadduct by means of chemical bonds, and is no longer removable by operations involving washing off.
  • Aliphatically attached hydroxyl groups have been determined to be particularly useful as reactive groups, and generally two of these groups are incorporated in the molecule.
  • the hydroxyl groups may be situated at the end of long chains obtainable by reaction with ethylene oxide or propylene oxide of dyes containing nucleophilic groups.
  • dyes are often liquid at room temperature and can be added in highly concentrated form to the foaming system (see for example US 4,284,729 and EP 0 166 566 A2).
  • the liquid nature of these dyes ensures ease of meterability and promotes good and rapid solubility in the initially charged polyurethane component. The latter is often problematical in the case of pulverulent or pasty dyes.
  • EP 0 837 082 A1 already discloses liquid reactive dyes with which polyurethane foams can be colored in orange shades.
  • the strength of the dyes described therein is limited since relatively long polyether chains are needed to obtain room temperature liquid products of sufficiently low viscosity.
  • the hereinbelow defined dyes of formula I according to the present invention provide relatively low-viscosity liquid products that are useful for coloring polyurethane in orange shades and that are superior in terms of strength to the dyes of EP 0 837 082 A1 at a given consistency.
  • the present invention accordingly provides azo dyes of formula I where
  • R is alkyl-O, aryl-O, alkyl-NH, dialkyl-N, aryl-NH, diaryl-N, where the alkyl and aryl groups can also be substituted;
  • X and X 1 are independently hydrogen, chlorine or bromine;
  • R 1 is hydrogen or methyl;
  • R 2 and R 3 are independently hydrogen or methyl; and n and m are independently a number from 2 to 100.
  • Alkyl groups may be straight chain or branched and they have 1 to 8 carbon atoms in particular. Examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and 2-ethylhexyl, of which methyl and ethyl are particularly preferred.
  • Substituted alkyl groups are preferably substituted by 1 , 2 or 3 substituents selected from the group consisting of phenoxy, (Ci-C 4 )alkoxy-(Ci-C 4 )alkoxy, (Ci-C 4 )alkoxy and hydroxy.
  • Aryl groups are in particular phenyl and naphthyl, of which phenyl is particularly preferred.
  • Substituted alkyl groups are preferably substituted by 1 , 2 or 3 substituents selected from the group consisting of methyl, ethyl, hydroxy and (Ci-C 4 )alkoxy.
  • R 2 and R 3 can be methyl as well as hydrogen within any one molecule.
  • the meanings of hydrogen and methyl can be randomly distributed along the entire side chain, but there can also be regions in which R 2 and R 3 are exclusively hydrogen or exclusively methyl.
  • the azo dyes of formula I according to the present invention are obtainable in a conventional manner.
  • the bromination can be effected with elemental bromine or bromine sources (for example sodium bromide/hydrogen peroxide) in organic solvents (for example acetic acid), in mineral acids or else without solvent in a conventional manner.
  • elemental bromine or bromine sources for example sodium bromide/hydrogen peroxide
  • organic solvents for example acetic acid
  • the monochlorinated compounds are advantageously obtainable with N-chlorosuccinimide by following T. E. Nickson et al., Synthesis 1985, 669-670.
  • the halogenation reactions mentioned give mixtures of the nonhalogenated, monohalogenated and bishalogenated 4-aminobenzoic acid derivatives of formula IV. These can be used in that form in the further synthesis, so that mixtures of azo dyes of formula I are obtained in this case. It is advantageous here that the hue desired for the resulting dye mixture can be fine tuned via the ratio of the individual components of formula II.
  • R 1 is as defined above
  • ethylene oxide and/or propylene oxide under base catalysis.
  • the reaction is preferably carried out first with propylene oxide and then with ethylene oxide, but the reverse procedure is also possible.
  • Ethylene oxide and propylene oxide can also be used concurrently, in which case they are incorporated in the polyether chains in a random manner.
  • the materials obtained through these reactions represent mixtures of compounds of various chain lengths and chain constitutions, in which the distribution of the molar masses approximately conforms to a Gaussian distribution.
  • the azo dyes of formula I are incorporable in the polyurethane polymer, with covalent bonds, by reaction of their terminal hydroxyl groups with isocyanate groups of the polyurethane-building blocks. They are therefore very useful for coloration of polyurethane, particularly polyurethane foams, in that they are notable for very high fastnesses to migration. High color strength is a further advantage of azo dyes of formula I, so that only small amounts are needed for coloration. In addition, the polyurethane system becomes only minimally adulterated with foreign substances, which minimizes the risk of foam disruptions.
  • the present invention accordingly also provides a process for producing colored polyurethane by polyaddition of a diol component with a diisocyanate component in the presence of a dye, wherein said dye is an azo dye of formula I
  • R is alkyl-O, aryl-O, alkyl-NH, dialkyl-N, aryl-NH, diaryl-N, where the alkyl and aryl groups can also be substituted;
  • X and X 1 are independently hydrogen, chlorine or bromine;
  • R 1 is hydrogen or methyl;
  • R 2 and R 3 are independently hydrogen or methyl; and n and m are independently a number from 2 to 100.
  • the polyaddition of the diol component with the diisocyanate component is carried out according to methods which have been previously described and which are known to one skilled in the art (see for example EP 0 166 566 A2 and the references cited therein).
  • the azo dye of formula I becomes incorporated in the polyurethane structure via covalent bonding through its hydroxyl groups.
  • the azo dye of formula I may be added to the reaction mixture of diol component and diisocyanate component before or during the polyaddition reaction. Preferably, however, the dye is added to the diol component before the diol component comes into contact with the diisocyanate component.
  • the azo dye of formula I is admixed to a polyether polyol or a polyester polyol and this preparation can then be used for the polyaddition with a diisocyanate.
  • the polyether polyols and polyester polyols contain at least two and preferably at least three hydroxyl groups.
  • Polyester polyols are obtainable for example by reaction of phthalic acid or adipic acid with polyalcohols, examples being glycol, diethylene glycol, thethylene glycol, 1 ,4-butanediol, glycerol or thmethylolpropane.
  • Polyether alcohols are obtained for example by ethehfying the aforementioned alcohols.
  • the diisocyanates may be aliphatic and aromatic in nature and may also contain more than two isocyanate groups.
  • Tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are the most common.
  • the ratio of polyol to diisocyanate depends on the molar masses, and it is normal to use a small excess of the diisocyanate.
  • the molar ratio of polyol to diisocyanate can be for example between 1 :0.85 to 1 :1.25. To produce more rigid foams, it is generally customary to use diisocyanate excesses of 100-300%.
  • the addition polymerization customarily utilizes stabilizers and activators or catalysts.
  • Preferred stabilizers are for example silicones, which may comprise between 0.1 % and 2% and preferably between 0.5% and 1.6% of the entire foam-forming mixture.
  • Possible activators are amines, preferably tertiary amines. They may comprise 0.05% to 1 % and preferably 0.07% to 0.6% of the mixture.
  • Polyurethane foam is produced according to the same principle, the foam being produced by the addition of blowing gas or by the addition of water to the diol/polyol component, leading to the formation of carbon dioxide blowing gas.
  • the production of colored polyurethane foams is described in detail in US 2004/0254335 for example.
  • Example 1 a An initial charge is prepared of 30.5 parts of methyl 4-aminobenzoate and 18.2 parts of sodium acetate (anhydrous) in 315 parts of acetic acid. The mixture is heated to 40 0 C, maintained at 40 0 C for 30 min and then cooled down to room temperature. A solution of 8 parts of bromine in 10.5 parts of acetic acid is added dropwise at 20-25°C during 30 min. The mixture is subsequently stirred at 20-25 0 C for 45 min and then admixed, at this temperature, with a solution of 4 parts of bromine in 5.2 parts of acetic acid added dropwise during 15 min. This is followed by stirring at room temperature for 16 h.
  • the bromination mixtures Mc to Me can be used in the procedure indicated in Example 1 b) to obtain the following azo dyes.
  • a polyether polyol obtained by etherification of butane-1 ,4-diol
  • a polyether polyol obtained by etherification of butane-1 ,4-diol
  • N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine) as catalyst are initially charged.
  • 1 part of the dye of Example 1 b) is added to the initial charge.
  • the mixture is intensively stirred by means of a dissolver disk for 20-30 sec.
  • 60 parts of diphenylmethane 4,4'-diisocyanate are speedily added before intensive mixing together for 7 sec by means of the dissolver disk.
  • the contents are then poured into a vessel to form the foam, for which cups made of paper or paperboard are suitable.
  • the components After about 5 min, the components will have reacted off and after a further 10 min the foam will have cured. It is allowed to cool down to room temperature. 20 min after cooling down, the foam can be sawn open to assess its hue. The foam obtained has a bright orange color, no foam disruptions and has very good washfastnesses.

Abstract

Cette invention concerne des colorants azoïques de formule (I). Dans la formule (I), R, X, X1, R1, R2, R3, n et m sont chacun tels que définis dans la revendication 1. L'invention concerne également des procédés pour les préparer et des procédés pour produire un polyuréthanne coloré.
PCT/EP2009/057644 2008-06-28 2009-06-19 Colorants azoïques pour la coloration des polyuréthannes WO2009156335A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008030795 2008-06-28
DE102008030795.5 2008-06-28

Publications (1)

Publication Number Publication Date
WO2009156335A1 true WO2009156335A1 (fr) 2009-12-30

Family

ID=40935537

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Application Number Title Priority Date Filing Date
PCT/EP2009/057644 WO2009156335A1 (fr) 2008-06-28 2009-06-19 Colorants azoïques pour la coloration des polyuréthannes

Country Status (2)

Country Link
TW (1) TW201002786A (fr)
WO (1) WO2009156335A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3088928A1 (fr) * 2018-11-27 2020-05-29 Chryso Méthode d’analyse de la quantité d’argile dans un sable

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284729A (en) * 1980-03-31 1981-08-18 Milliken Research Corporation Process for coloring thermosetting resins
US4751254A (en) * 1987-01-20 1988-06-14 Milliken Research Corporation Process for in situ coloration of thermosetting resins
US4812141A (en) * 1985-09-13 1989-03-14 Milliken Research Corporation Colored thermoplastic resin composition
US5043013A (en) * 1987-12-30 1991-08-27 Milliken Research Corporation Washable ink compositions
EP0837082A1 (fr) * 1996-10-18 1998-04-22 Milliken Research Corporation Procédé de coloration des résines de polymères et ses produits colorés

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284729A (en) * 1980-03-31 1981-08-18 Milliken Research Corporation Process for coloring thermosetting resins
US4812141A (en) * 1985-09-13 1989-03-14 Milliken Research Corporation Colored thermoplastic resin composition
US4751254A (en) * 1987-01-20 1988-06-14 Milliken Research Corporation Process for in situ coloration of thermosetting resins
US5043013A (en) * 1987-12-30 1991-08-27 Milliken Research Corporation Washable ink compositions
EP0837082A1 (fr) * 1996-10-18 1998-04-22 Milliken Research Corporation Procédé de coloration des résines de polymères et ses produits colorés

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3088928A1 (fr) * 2018-11-27 2020-05-29 Chryso Méthode d’analyse de la quantité d’argile dans un sable

Also Published As

Publication number Publication date
TW201002786A (en) 2010-01-16

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