TW201002786A - Azo dyes for coloration of polyurethanes - Google Patents

Abstract

The present invention concerns azo dyes of formula I where R, X, X1, R1, R2, R3, n and m are each as defined in claim 1, processes for their preparation and processes for producing colored polyurethane.

Description

201002786 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to an azo dye for coloring a polyurethane. [Prior Art] A polyurethane-based artificial polymer obtained by a polymerization addition reaction of a structural unit containing at least two hydroxyl groups, and is known as a structural unit having at least two isocyanate groups Glycols, and are known as diisocyanates. Polyurethanes are generally produced by the incorporation of specific water during the polycondensation to form carbon dioxide, or by adding a gas from the outside as a foam. Colored polyurethanes are generally produced by mixing one of the two components (ie, a diol) with a dye (diisocyanate) containing at least one functional group capable of reacting with another component to form a covalent bond. of. Therefore, the dye is incorporated into the polyadduct in a chemical bond and is no longer removable in handling (including washing). Adipose-linked hydroxyl groups have been identified as being particularly useful as reactive groups, and typically two of these groups are incorporated into the molecule. The hydroxyl group may be located at the end of the long chain which is obtainable by the reaction of the nucleophilic group-containing dye with ethylene oxide or propylene oxide. Such dyes are often liquid at room temperature and can be added to the foaming system in a highly concentrated form (see, for example, US 4,284,729 and EP 0 166 566 A2). The liquid nature of the dyes ensures metering simplicity and improves their good and rapid solubility in the first fed polyurethane component. In the case of powdery or -5-201002786 mushy dyes, the latter is often tricky. EP 0 837 082 A1 has disclosed a class of liquid reactive dyes with which polyurethane foams can be dyed in an orange hue. However, there is a need for relatively long polyether chains to obtain a product having a sufficiently low viscosity, wherein the strength of the dyes described is limited. Surprisingly, it has now been found that the dyes of formula I according to the invention defined below provide a relatively low viscosity liquid product which is useful for dyeing polyurethanes in orange tones and in terms of strength. The class of products is superior to the dyes of EP 0 837 082 A1 at a given consistency. SUMMARY OF THE INVENTION Accordingly, the present invention provides a chemical formula 1

Azo dyes wherein R is alkyl-0, aryl-hydrazine, alkyl-NH, dialkyl-N, aryl-NH, diaryl-N, wherein the groups of the aryl and aryl groups May 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 -6- 201002786 η and m are independently from 2 Number to 100. The alkyl groups may be straight or branched, and in particular they have from 1 to 8 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and 2-ethylhexyl, of which methyl and B The base system is particularly preferred. The substituted alkyl group is preferably substituted by 1, 2 or 3 substituents which are selected from the group consisting of phenoxy, (CKC4) alkoxy-(C丨-C4) Alkoxy, (alkoxy, and hydroxy. The aryl group is especially phenyl and naphthyl, wherein phenyl is particularly preferred. The substituted alkyl group is preferably 1, 2 or 3 substituents. Substituting 'the substituent is selected from the group consisting of methyl, ethyl, hydroxy and (C!-C4) alkoxy. In Formula I, 1» and n are derived from the epoxy used in the preparation. The average enthalpy of the equivalents of ethane (R2 and R3 = hydrogen) or propylene oxide (R2 and R3 = methyl). m and η are each preferably 2 to 2 0. In any molecule, 'R2 and R3 can It is a methyl group and hydrogen. The meaning of hydrogen and methyl is that they can be randomly distributed along the entire side chain, but there may be some regions in which R2 and R3 are only hydrogen or only methyl. Formula according to the invention The azo dye of I can be obtained by a conventional method. For example, a compound of the formula II

(II) 201002786 wherein R, X and X1 are each independently diazotized and coupled to a compound of formula III as defined above.

(III) wherein R1, R2, R3, m and η are each as defined above. After the reaction has taken place, the azo dye of formula I can be removed from the reaction medium with a water-immiscible organic solvent. After drying and evaporation of the solvent, a free flowing orange dye oil was obtained. A compound of formula II wherein at least one of X and X1 is other than hydrogen is obtained by halogenating a compound of formula IV

(IV) wherein R is as defined above. When X and/or X 1 represents bromine, it may be conventionally carried out with an elemental bromine or a source of bromine (for example sodium bromide/hydrogen peroxide) in an organic solvent such as acetic acid, a mineral acid or otherwise without a solvent. Complete bromination. When one of X and X1 represents chlorine, the monochlorinated compound is advantageously obtained by using N-chlorosuccinimide according to the literature τ·E_ Nickson et al., Synthesis 1985, 669-670. In summary, the halogenation reaction mentioned gives an unhalogenated, monohalogenated, and dihalogenated 4-aminobenzoic acid derivative of the formula IV 201002786. These derivatives can be used in this form in further synthesis, such that a mixture of azo dyes of formula I is obtained in this case. It is advantageous here that the desired color tone for the resulting dye mixture can be finely tuned by the ratio of the individual components of formula II. Compounds of formula III can likewise be obtained by methods known from the literature (see example US 3,157,633). To this end, a compound of formula V is obtained in the presence of a basic catalyst

(wherein R1 is as defined above) is reacted with ethylene oxide and/or propylene oxide. 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 simultaneously, in which case they are incorporated into the polyether chain in a random manner. The materials obtained by such reactions represent a mixture of compounds having different chain lengths and chain structures, wherein the distribution of the molar mass generally follows a Gaussian distribution. Thus, the chemical formula described in this patent application describes an average enthalpy derived from the equivalent of ethylene oxide and propylene oxide used. This average enthalpy also roughly corresponds to the molar mass obtained from the average determined in gel permeation chromatography. The average number of equivalents of ethylene oxide and propylene oxide -9 - 201002786 can also be determined from the integral of the H NMR spectrum. The azo dyes of the formula I are reacted with the isocyanate groups of the polyurethane-structural unit by their terminal hydroxyl groups, and can be incorporated into the polyurethane polymer by covalent bonds. Therefore, they are useful for the coloring of polyurethanes, particularly polyurethane foams, in which they are known for their very high fastness to color shift. A high color strength is an additional advantage of the azo dye of Formula I, such that coloration requires only a small amount. In addition, the polyurethane system is only minimally doped with foreign materials, which minimizes the risk of foam collapse. Thus, 'the present invention also provides a method for producing a colored polyurethane' which is carried out by the polymerization addition of a diol component and a diisocyanate component in the presence of a dye, wherein Dye is an azo dye of formula I

Wherein R is alkyl-hydrazine, aryl-0, alkyl-NH, dialkyl-N, aryl-NH, diaryl-N' wherein the alkyl and aryl groups may be substituted x and X1 are independently hydrogen, chlorine or bromine; R1 is hydrogen or methyl; -10- 201002786 R2 and R3 are independently hydrogen or methyl; and η and in are independently numbers from 2 to 100. The polymerization addition of the diol component to the diisocyanate is carried out according to the methods described and methods well known to those skilled in the art (Example ΕΡ 0 1 66 566 Α 2 and references cited therein). In the process of polymerization addition, the azo dye of formula I can be incorporated into the structure of the polyurethane by covalent bonding of its hydroxyl group. The azo dye of formula I can be in the process of polymerization addition reaction. The reaction of adding the diol component and the diisocyanate component is mixed. Preferably, however, the dye is added to the diol component prior to contacting the diol component with the diisocyanate. In a preferred aspect, the azo dye of formula I is mixed with a polyether polyol or a polyester polyol and such an article is used for the polymerization addition to the diisocyanate. The polyether polyol and polyester polyol comprise at least two and at least three hydroxyl groups. The polyester polyol can be obtained, for example, by the reaction of phthalic acid or oxalic acid with a polyhydric alcohol. Examples of the polyhydric alcohol are alcohol, diethylene glycol, triethylene glycol, 1,4-butanediol, and C3. Alcohol or triethylpropane. The polyether alcohol is obtained, for example, by etherification of the aforementioned alcohol. The diisocyanates may be aliphatic and aromatic in nature and may also contain more than two isocyanate groups. The ratio of toluene diisocyanide (TDI) to diphenyl carbene diisocyanate (MDI), the most common ratio of white and polyhydric alcohol to diisocyanate, depends on the Moir mass, and has been previously referred to the feed IJ or compound. The ester group is preferably a good afterglycol formate and the ester f 〇 and it is normal to use a slight excess of diisocyanate for -11 - 201002786. The molar ratio of the polyol to the diisocyanate may be, for example, between 1: 〇 _ 8 5 to 1: 1.2 5. In order to produce a harder foam, it is conventional to use an excess of 100-300% diisocyanate. Addition polymerization is conventionally the use of stabilizers as well as activators or catalysts. Preferred stabilizers are, for example, organoindoles which may comprise between 0.1% and 2% of the total foaming mixture, preferably between 5% and 1.6%. Possible activators are amines, preferably tertiary amines. They may comprise 〇 〇 5% to 1% and preferably 0. 〇 7 % to 0 · 6 %. The polyurethane foam is produced according to the same principle, which is produced by adding blast gas or adding water to the diol/polyol component to form a carbon dioxide blast gas. The production of colored polyurethane foams is described in detail, for example, in US 2004/0254335. Thus, by using an azo dye of the formula I, it is possible to produce a polyurethane foam which is free from cracking in the foam structure and which has good non-fading properties, which also forms part of the subject matter of the present invention. [Embodiment] The following examples are given to illustrate the present invention. The number of parts is by weight. Example 1 a) The first charge was prepared from 30.5 parts of methyl 4_ammonia-12-201002786-based benzoate and 18.2 parts of sodium acetate (anhydrous) in 315 parts of acetic acid. The mixture was heated to 40. C ' is at 40. C was held for 30 minutes' and then the mixture was cooled to room temperature. A solution of 8 parts of bromine in 10.5 parts of acetic acid was added dropwise at 20-25 ° C over 30 minutes. Subsequently, the mixture was stirred at 20-20 ° C for 45 minutes and then at this temperature the mixture was mixed with 4 parts of bromine in 5.2 parts of acetic acid, which solution was dropped in 15 minutes. Join. It was then stirred at room temperature for 16 h. Subsequent additions were carried out five more times, in each case 4 parts of bromine dissolved in 5.2 parts of acetic acid were added dropwise over 15 minutes at 20-25 °C. After each addition, the mixture was stirred at 20-25 ° C for 3 h. After the last addition, the mixture was stirred at 20-25 ° C for 16 h, and then 200 parts of ice was added. After that, 16.2 parts of a 40% sodium hydrogen sulfite solution was added, and then the mixture was stirred at 20 - 25 ° C for 30 minutes. The reaction mixture was then poured onto 2,500 parts of ice-water mixture and then stirred for 2 h. It was suction filtered and washed with water and dried, leaving 47.15 portions of white solid. It consists of a mixture comprising about 80% of a compound of formula Ila

And about 20% of the compound of formula 11b'

Br ( 11 b ) -13- 201002786 These two compounds are partially present in the form of their hydrobromides. b) 9.2 parts of the mixture obtained according to a) were introduced into 29.4 parts of 18% hydrochloric acid, followed by cooling to 0 °C. 7.68 parts of 40% sodium nitrite solution was added dropwise at 〇-4 ° C over 1.5 h. The mixture was then stirred at 〇 ° C for 3 h. After this, the excess nitrite was filtered and removed with a small amount of sulfamic acid. Coupling of 55.2 parts of N,N-bis(hydroxyethyl) m-toluidine and 20 equivalents of propylene oxide (P〇) and 7 equivalents of ethylene oxide (EO) as described in US 3,157,633 The agent was initially added to 280 parts ice-water and below 0. Under the conditions of C, it is mixed with the above diazotized mixture. The mixture was then stirred at 0 ° C for 2 h ' and then adjusted to p Η 7 with about 44 parts of a 30% aqueous sodium hydroxide solution. After this, the organic phase of the combined organic phase was washed with water and dried over sodium sulfate and the solvent was removed with a rotary evaporator, leaving 61 parts of the chemical formula la in the form of an orange oil. Nitrogen dye (λ max (DMF) = 4 7 8 nm )

Ο—Η

Where; X = 8 4 % Η, 16% Β r Example 2 to 9 Bromination mixture IIc to lie is similar to Example 1 a and obtains -14 - 201002786 R' X Xi RX = Br, Xi = H ratio [ %] X - Br, Xi = Br ratio [%] Form lie Ph0CH2CH20 85 15 Solid lid Me0CH2CH20CH2CH20 80 20 Solid lie 2-ethylhexyl-NH 85 15 Oil bromination mixture lie to lie can be in the procedure described in Example lb) Used to obtain the following azo dyes. The compound of formula III is in each case according to US 3,1 5 7,63 3 from hydrazine, hydrazine-bis(hydroxyethyl) m-toluidine (R1 = Me) or hydrazine, hydrazine-bis (hydroxyl) a compound obtained by reacting aniline (R1 = Η) with the indicated equivalents of propylene oxide (oxime) and ethylene oxide (Ε Ο). -15- 201002786 0--Η.斗令 C; "R. [Chemical + Jy Example RX X1 R1 s+t x+y λ max (DMF) M 2 MeO Cl H Me 20 7 480 3 MeO HH Me 31 0 462 4 MeO Br 85% H 15% Br H 20 7 470 5 Ph0CH2CH20 Br 85% H 15%Br Me 20 7 476 6 Me0CH2CH20CH2CH20 Br 78% H 22% Br Me 20 7 478 7 Me0CH2CH20CH2CH20 Br 83% H 17% Br Me 10 0 478 8 Me0CH2CH20CH2CH20 Br 96% H 4% Br Me 6 0 482 9 2-ethylhexyl-NH Br 85% H 15%Br Me 20 7 460 All of the dyes of Examples 2 to 9 constitute a free-flowing orange oil. Example 1 100 parts of polyether Type polyol (obtained by etherification of butane-1,4-diol) containing 1% by weight of hydrazine, hydrazine, hydrazine, Ν'-tetramethyl-2,2'-oxygen (ethylamine) as a catalyst, the first addition is carried out. One part of the dye of real-16-201002786 case 1 b) is added to the first charge. Subsequently, the mixture is thoroughly stirred by means of a dissolver pan for 20-30 seconds. The plates were thoroughly mixed together for 7 seconds before 'quickly adding 6 parts of diphenylmethane 4,4,-diisocyanate. Then the contents were poured into a container to form a foam, for which paper or hard The cup made of the plate is suitable. After about 5 minutes, the component will be reacted' and after 10 minutes, the foam will solidify. Allow it to cool to room temperature. After 20 minutes of cooling, it can be The foam was opened to evaluate its hue. The resulting foam had a bright orange color, no foam breakage and very good wash resistance. Repeating the foaming process described for the dyes of Examples 2 to 9 also gave no foam breakage. And orange foam with very good washing resistance 0 -17-

Claims (1)

201002786 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to an azo dye for coloring a polyurethane. [Prior Art] A polyurethane-based artificial polymer obtained by a polymerization addition reaction of a structural unit containing at least two hydroxyl groups, and is known as a structural unit having at least two isocyanate groups Glycols, and are known as diisocyanates. Polyurethanes are generally produced by the incorporation of specific water during the polycondensation to form carbon dioxide, or by adding a gas from the outside as a foam. Colored polyurethanes are generally produced by mixing one of the two components (ie, a diol) with a dye (diisocyanate) containing at least one functional group capable of reacting with another component to form a covalent bond. of. Therefore, the dye is incorporated into the polyadduct in a chemical bond and is no longer removable in handling (including washing). Adipose-linked hydroxyl groups have been identified as being particularly useful as reactive groups, and typically two of these groups are incorporated into the molecule. The hydroxyl group may be located at the end of the long chain which is obtainable by the reaction of the nucleophilic group-containing dye with ethylene oxide or propylene oxide. Such dyes are often liquid at room temperature and can be added to the foaming system in a highly concentrated form (see, for example, US 4,284,729 and EP 0 166 566 A2). The liquid nature of the dyes ensures metering simplicity and improves their good and rapid solubility in the first fed polyurethane component. In the case of powdery or -5 - 201002786 mushy dyes, the latter is often tricky. E P 0 8 3 7 0 8 2 A1 has revealed a class of liquid reactive dyes with which polyurethane foams can be dyed in an orange hue. However, because of the relatively long polyether chains required to obtain room temperature liquid products having sufficiently low viscosities, the strength of such dyes described therein is limited. Surprisingly, it has now been found that the dyes of formula I as defined hereinafter in accordance with the invention provide relatively low viscosity liquid products which are useful for dyeing polyurethanes in orange shades and which are in terms of strength. It is superior to the dye in EP 0 8 3 7 0 8 2 A 1 at a given consistency. SUMMARY OF THE INVENTION Accordingly, the present invention provides an azo dye having the chemical formula I Wherein R is alkyl-0, aryl-hydrazine, alkyl_NH, dialkyl-N, aryl_NH, diaryl-Ν' wherein the alkyl and aryl groups may be substituted X and X 1 are hydrogen, chlorine or bromine alone; R1 is hydrogen or methyl; R2 and R3 are independently hydrogen or methyl; and -6-201002786 η and m are independently numbers from 2 to 100. . The todenyl groups may be straight or branched, and in particular they have from 1 to 8 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and 2-ethylhexyl, of which methyl and B The base system is particularly preferred. The substituted alkyl group is preferably substituted by 1, 2 or 3 substituents selected from the group consisting of phenoxy, (CKC4) alkoxy-(Cl_c4) alkoxy. , (Cl-C4) alkoxy group and hydroxyl group. The aryl group is especially phenyl and naphthyl, with phenyl being especially preferred. The substituted alkyl group is preferably substituted by 1, 2 or 3 substituents which are selected from the group consisting of methyl, ethyl, hydroxy and (C!-C4) alkoxy groups. . In the formula I, 'm and n are derived from the average enthalpy of the equivalents of ethylene oxide (R2 and R3 = hydrogen) or propylene oxide (R2 and R3 = methyl) used in the preparation. m and η are each preferably 2 to 20. In any molecule, R2 and R3 may be a methyl group and hydrogen. The meaning of hydrogen and methyl is that they can be randomly distributed along the entire side chain, but there may be some regions in which R2 and R3 are exclusively hydrogen or only methyl. The azo dye of the formula I according to the present invention can be obtained by a conventional method. For example, a compound of formula II (II) 201002786 wherein R, X and X1 are each diazotized and coupled to a compound of formula III as defined above (III) wherein R1, R2, R3, m and η are each as defined above. After the reaction has taken place, the azo dye of formula I can be removed from the reaction medium with a water-immiscible organic solvent. After drying and evaporation of the solvent, a free flowing orange dye oil was obtained. A compound of formula II wherein at least one of X and X1 is other than hydrogen is obtained by halogenating a compound of formula IV (IV) wherein R is as defined above. When X and/or X1 represents bromine, it can be carried out in a conventional manner by using an elemental bromine or a source of bromine (for example sodium bromide/hydrogen peroxide) in an organic solvent such as acetic acid, a mineral acid or otherwise without a solvent. Bromination. When one of X and X1 represents chlorine, the monochlorinated compound is advantageously obtained by using N-chlorosuccinimide according to the literature Τ·E. Nickson et al, Synthesis 1985, 669-670. In summary, the halogenation reaction mentioned gives an unhalogenated, monohalogenated, and dihalogenated 4-aminobenzoic acid derivative of the formula IV 201002786. These derivatives can be used in this form in further synthesis, such that a mixture of azo dyes of formula I is obtained in this case. It is advantageous here that the desired color tone for the resulting dye mixture can be finely tuned by the ratio of the individual components of formula II. Compounds of formula III can likewise be obtained by methods known from the literature (see example US 3,157,633). For this purpose, a compound of formula V is present in the presence of a basic catalyst (wherein R1 is as defined above) is reacted with ethylene oxide and/or propylene oxide. 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 simultaneously, in which case they are incorporated into the polyether chain in a random manner. The materials obtained by such reactions represent a mixture of compounds having different chain lengths and chain structures, wherein the distribution of the molar mass generally follows a Gaussian distribution. Thus, the chemical formula described in this patent application describes an average enthalpy derived from the equivalent of ethylene oxide and propylene oxide used. This average enthalpy also roughly corresponds to the molar mass obtained from the average determined in gel permeation chromatography. The average of the equivalents of ethylene oxide and propylene oxide -9-201002786 can also be determined from the integral of the 1H NMR spectrum. The azo dyes of the formula I are reacted with the isocyanate groups of the polyurethane-structural unit by their terminal hydroxyl groups, and can be incorporated into the polyurethane polymer by covalent bonds. Therefore, they are useful for the coloring of polyurethanes, particularly polyurethane foams, in which they are known for their very high fastness to color shift. A high color strength is an additional advantage of the azo dye of Formula I, such that coloration requires only a small amount. In addition, the polyurethane system is only minimally doped with foreign matter, which minimizes the risk of foam collapse. Accordingly, the present invention also provides a process for producing a colored polyurethane which is carried out by polymerization addition of a diol component and a diisocyanate component in the presence of a dye, wherein Dye is an azo dye of formula I Wherein R is a group-0, an aryl group, an anthracene group -NH, a second group of a group -N, an aryl group NH, a group of groups _N' wherein the groups of the substituents and aryl groups may be substituted; X and X 1 are independently hydrogen, chlorine or bromine; R 1 is hydrogen or methyl; -10- 201002786 R 2 and R 3 are independently hydrogen or methyl; and η and m are independently numbers from 2 to 100. The polymerization addition of the diol component to the diisocyanate is carried out according to the methods already described and methods well known to those skilled in the art (see the example EP 0 1 66 5 66 A2 and the references cited therein). . During the polymerization addition, the azo dye of formula I can be incorporated into the structure of the polyurethane via covalent bonding of its hydroxyl group. The azo dye of the formula I may be added to the reaction mixture of the diol component and the diisocyanate component before or during the polymerization addition reaction. Preferably, however, the dye is added to the diol component prior to contacting the diol component with the diisocyanate component. In a preferred aspect, the azo dye of Formula I is mixed with a polyether polyol or a polyester polyol, and such an article can be used later for polymerization addition to the diisocyanate. The polyether polyol and polyester polyol comprise at least two and preferably at least three hydroxyl groups. The polyester polyol can be obtained, for example, by the reaction of phthalic acid or oxalic acid with a polyhydric alcohol. Examples of the polyhydric alcohol are ethylene glycol, diethylene glycol, triethylene glycol, and 1,4-butanediol. , glycerol or trimethylolpropane. The polyether alcohol is obtained, for example, by etherification of the aforementioned alcohol. The diisocyanates may be aliphatic and aromatic in nature and may also contain more than two isocyanate groups. Toluene diisocyanate (TDI) and diphenylmethyl diisocyanate (MDI) are the most common. The ratio of polyol to diisocyanate depends on the Mohr mass' and it is also normal to use a slight excess of diisocyanate for -11 - 201002786. The molar ratio of the polyol to the diisocyanate may be, for example, between 1: 〇 _ 8 5 to 1: 1.5. In order to produce a harder foam, it is conventional to use an excess of from 1 to 30% of diisocyanate. Addition polymerization is conventionally the use of stabilizers as well as activators or catalysts. Preferred stabilizers are, for example, organoindoles which may include 0.1 °/ of the entire foam forming mixture. Between 2%, preferably between 0.5% and 1.6%. Possible activators are amines, preferably tertiary amines. They may comprise from 0.05% to 1% and preferably from 0.07% to 0.6% of the mixture. The polyurethane foam is produced according to the same principle, which is produced by adding blast gas or adding water to the diol/polyol component to form a carbon dioxide blast gas. The production of colored polyurethane foams is described in detail, for example, in US 2004/0254335. Thus, by using an azo dye of the formula I, it is possible to produce a polyurethane foam which is not cracked in the foam structure and which has good color resilience, which also forms part of the subject matter of the present invention. [Embodiment] The following examples are given to illustrate the present invention. The number of parts is by weight. Example 1 a) The first feed was prepared from 30.5 parts of methyl 4-ammonium-12-201002786-based benzoate and 18.2 parts of sodium acetate (anhydrous) in 315 parts of acetic acid. The mixture was heated to 4 (TC, held at 40 ° C for 30 minutes' and then the mixture was cooled to room temperature. At 20-25 ° C, a solution of 8 parts of bromine in 10.5 parts of acetic acid was added dropwise over 30 minutes. Subsequently, the mixture was stirred at 20 to 2 ° C for 45 minutes, and then at this temperature, the mixture was mixed with 4 parts of a solution of bromine in 5.2 parts of acetic acid, the solution was within 15 minutes. Add dropwise, then at room temperature for 16 h. Then add five more times, in each case, at 20-25 ° C, 4 parts of bromine dissolved in 5.2 parts of acetic acid in drops for 15 minutes After the addition, the mixture was stirred at 20-25 ° C for 3 h. After the last addition, the mixture was stirred at 20-25 ° C for 16 h, and then 200 parts of ice was added. Thereafter, 16.2 parts of a 40% sodium hydrogen sulfite solution was added, and then the mixture was stirred at 20 _ 25 C for 3 Torr. The reaction mixture was then poured onto 2500 parts of ice-water mixture. , then stirred for 2 h. Filtered with suction, washed with water and dried, leaving 47.15 portions of white solid. Into, the mixture comprises from about 80% of the compound of formula Ila And about 20% of the compound of formula 11b, (Hb) -13- 201002786 These two compounds are partially present in the form of their hydrobromides. b) 9.2 parts of the mixture obtained according to a) are introduced into 29.4 parts of 18% hydrochloric acid, after which it is cooled to 〇 °C. 7.68 parts of 40% sodium nitrite solution was added dropwise at 〇4 ° C for 1_5 h. The mixture was then stirred at 〇 ° C for 3 h. After this, the excess nitrite was filtered and removed with a small amount of sulfamic acid. Coupling of 55.2 parts of N,N-bis(hydroxyethyl) m-toluidine and 20 equivalents of propylene oxide (P〇) and 7 equivalents of ethylene oxide (EO) as described in US 3,157,633 The agent was initially added to 280 parts of ice-water and below 0. Under the conditions of C, it is mixed with the above diazotized mixture. Then at 0. C The mixture was stirred for 2 h' and then adjusted to pH 7 with about 4 4 parts of a 30% aqueous sodium hydroxide solution. After this, the organic phase of the combined organic phase was washed with water and dried over sodium sulfate, and the solvent was removed with a rotary evaporator, leaving 61 parts of the formula Ia in the form of an orange oil. Nitrogen dye (λ max (DMF) = 478 nm ) Where X = 8 4 % Η, 16 % B r Examples 2 to 9 Brominated mixture 11 c to 11 e Similar to Example 1 a to obtain -14 - 201002786 R, X ^~^-nh2 Xi RX = Br , Xi = H ratio [%] X = Br, X, = Br ratio [%] Form He Ph0CH2CH20 85 15 Solid lid MeOCH2CH2OCH2CH20 80 20 Solid lie 2-ethylhexyl-NH 85 15 Oil bromination mixture lie to lie can be Example 1 b) was used in the procedure described to obtain the following azo dyes. The compounds of the formula 在 are in each case according to US 3,1 5 7,6 3 3 from hydrazine, Ν-bis(hydroxyethyl) m-toluidine (R1 = Me) or hydrazine, hydrazine-di(hydroxyl) A compound obtained by reacting ethyl phenylamine (R1 = H) with the indicated equivalents of propylene oxide (oxime) and ethylene oxide (oxime). -15- 201002786 0--Η.吟 "R. [Heart 0--Η Jy Example RX X1 R1 s+t x+y λ max (DMF) "nml 2 MeO Cl H Me 20 7 480 3 MeO HH Me 31 0 462 4 MeO Br 85% H 15 % Br H 20 7 470 5 Ph0CH2CH20 Br 85% H 15% Br Me 20 7 476 6 Me0CH2CH20CH2CH20 Br 78% H 22% Br Me 20 7 478 7 MeOCH2CH2OCH2CH20 Br 83% H 17% Br Me 10 0 478 8 Me0CH2CH20CH2CH20 Br 96% H 4% Br Me 6 0 482 9 2-ethylhexyl-NH Br 85% H 15% Br Me 20 7 460 All of the dyes of Examples 2 to 9 constitute a free-flowing orange oil. Example 10 100 parts of polyether Type polyol (obtained by etherification of butane-1,4-diol) containing 1% by weight of hydrazine, hydrazine, hydrazine ', N'-tetramethyl-2,2'-oxygen (ethylamine) as a catalyst, the first addition was carried out. 1 part of the dye of the solid-16 - 201002786 case 1 b) was added to the first charge. Subsequently, the mixture was thoroughly stirred by means of a dissolver disk for 20.3 0 seconds. 60 parts of diphenylmethane 4,4'-diisocyanate were quickly added before the trays were thoroughly mixed together for 7 seconds, and then the contents were poured into a container to form a foam. A cup made of paper or cardboard is suitable. After about 5 minutes, the component will be reacted, and after another 1 minute, the foam will solidify. Allow it to cool to room temperature. After cooling 2 After 0 minutes, the foam can be opened to evaluate its hue. The resulting foam has a bright orange color, no foam breakage and very good wash resistance. The foaming process described for the dyes of Examples 2 to 9 is repeated the same. An orange foam having no foam breakage and having very good washing resistance is given. Repeating the foaming process described for the dyes of Examples 2 to 9 also gives no foam breakage and very good washing resistance. Orange foam -17- 201002786 VII. Patent application scope 1. Azo dyes with chemical formula (I) Wherein R is alkyl-hydrazine, aryl-hydrazine, alkyl-NH, dialkyl-N, aryl-NH, diaryl-N, wherein the groups of the alkyl and aryl groups may 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 η and m are independently numbers from 2 to 1 0. 2. A method for preparing an azo dye having the formula (I) as described in claim 1, wherein the method comprises a compound having the formula (Π) Wherein R, X and X1 are each as defined in the scope of claim 1, the compound is diazotized and coupled to a compound of the formula (ΠΙ) -18- 5-201002786 〇 /~f N 0· (III) Wherein R·1, R·2, r3, m and are defined. 3. A method for producing a colored polyurethane, which is carried out by a polymerization addition reaction of a diol component with a diisocyanate component in the presence of a dye, wherein the dye has Azo dye of formula (I) Wherein R is alkyl-hydrazine, aryl-hydrazine, alkyl-NH, dialkyl-N, aryl-NH, diaryl-Ν' wherein the alkyl and aryl groups may also be substituted X and X1 are independently nitrogen, chlorine or desert; R1 is hydrogen or methyl; R2 and R3 are independently hydrogen or methyl; and η and m are independently numbers from 2 to 100. 4. The method of claim 3, wherein the polyurethane is produced in the form of a foam. 5. —Colored polyurethane' which is colored with a nitrogen dye of the formula -19-201002786 Wherein - the group of the group -N, the aryl group - may also be taken as R-alkyl-hydrazine, aryl-hydrazine, alkyl-NH, NH, diaryl-N, wherein the % of the base and the square X and X1 are independently hydrogen, chlorine or bromine; R 1 is hydrogen or methyl; R 2 and R 3 are independently hydrogen or methyl; and η and m are independently numbers from 2 to 10. -20- 201002786 VII. Patent application scope 1. Azo dye with chemical formula (I) Wherein R is alkyl-0, aryl-0, alkyl-NH, dialkyl-N, aryl-NH, diaryl-N, wherein the groups of the alkyl and aryl groups may also be substituted X and X 1 are independently hydrogen, chlorine or bromine; R 1 is a gas or a methyl group; R 2 and R 3 are independently hydrogen or methyl; and η and m are independently numbers from 2 to 1 0. 2. A method for preparing an azo dye having the formula (I) as described in claim 1, wherein the method comprises a compound having the formula (Π) Wherein R, X and X1 are each as defined in the scope of claim 1, the compound is diazotized and coupled to a compound of the formula (III) 201002786 And n are each as defined in the series of patents 1 wherein Rl, R2, r3. 3. A method for producing a colored polyurethane 曰 万, which is carried out by a polymerization reaction of a diol component with a S-isocyanate component in the presence of a dye, wherein An azo dye of the formula (I) Wherein R is a group of base-0, aryl-0, a group of the group -NH, a second group of -N, an aryl-NH, a diaryl-N, wherein the groups of the alkyl and aryl groups may 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 η and m are independently numbers from 2 to 100. 4. The method of claim 3, wherein the polyurethane is produced in the form of a foam. 5. —Colored polyurethane, which is colored with a nitrogen dye of the formula -19-201002786 The group of the dialkyl-N, aryl- group may also be taken as R-alkyl-hydrazine, aryl-hydrazine, alkyl-NH, NH, diaryl-N, wherein the alkyl and aryl groups Generation; X and X 1 are independently hydrogen, chlorine or bromine; R1 is hydrogen or methyl; R2 and R3 are independently hydrogen or methyl; and η and m are independently numbers from 2 to 10< 20- 201002786 Four designated representative figures: (1) The designated representative figure of this case is: None (2), the symbol of the representative figure is simple: No 201002786 If there is a chemical formula in the case, please reveal the chemical formula that best shows the characteristics of the invention. :Form (I) -4- 201002786 859315 i Ί ;! Invention patent specification (this application surface type ' (I word 'IfM壬 pasta> ※言雕 ※Application number: <?(Ρ· /; ;r ※Application date: (※)(:Classification : 1. Name of the invention: (Chinese / English) Azo dye for polyurethane coloring II. Abstract: The present invention relates to an azo dye having the chemical formula (I) Wherein R, X, X1, R1, R2, R3, η and m are each as defined in the first item of the patent application, and also relate to a method for producing the azo dye and a method for producing a colored polyurethane. 201002786 859315 i Ί ;! Invention patent specification (this application surface type ' (I word 'IfM壬 pasta> ※言雕 ※Application number: <?(Ρ· /; ;r ※Application date: (※)(:Classification : 1. Name of the invention: (Chinese / English) Azo dye for polyurethane coloring II. Abstract: The present invention relates to an azo dye having the chemical formula (I) Wherein R, X, X1, R1, R2, R3, η and m are each as defined in the first item of the patent application, and also relate to a method for producing the azo dye and a method for producing a colored polyurethane. 201002786 III. Abstract of English invention: The present invention concerns azo dyes of formula I 112 3 where R, X, X, R, R, R, n and m are each as defined in claim 1, processes for their preparation and processes for producing colored polyurethane. 201002786 IV. Designated representative map: (1) The representative picture is: None (2), the symbol of the symbol of this representative figure is simple: No 201002786 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (I) -4-