FR2574791A1 - FATTY AMINO ACID SULFATES, THEIR PREPARATION AND THEIR USE AS AUXILIARY PRODUCTS - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS THE COMPOUNDS OF FORMULA I: (CF DRAWING IN BOPI) IN WHICH R REPRESENTS AN ALKYL OR ALCENYL GROUP IN CC, R HYDROGEN, SODIUM, POTASSIUM, AN AMMONIUM GROUP OR A SUBSTITUTE AMMONIUM GROUP, R HYDROGEN OR A -SOR GROUP, M MEANS 2, 3 OR 4, AND NP 17 TO 23 INCLUDED. THESE COMPOUNDS MAY BE USED AS AUXILIARY PRODUCTS FOR DYING OR PRINTING SUBSTRATES CONTAINING NATURAL OR SYNTHETIC POLYAMIDE FIBERS.

Description

The subject of the present invention is new sulphates

  fatty amines, their preparation and their use as pro-

  auxiliary dyes for dyeing or printing substrates

  comprising natural or synthetic polyamide fibers.

  In particular, the invention relates to compounds of the formula I (CH 2mO) S 3 R 2 (I) wherein R 1 is C 18 -C 22 alkyl or C 18 alkenyl -C22, R2 represents hydrogen, sodium, potassium, an ammonium group or a substituted ammonium group, R3 represents hydrogen or a group -SO3R2, in each unit (CmH2mO =, m means 2, 3 or 4, and the sum n + p is between 17 and 23 inclusive,

  in basic form or in protonated or quaternized form.

  When R 1 represents a C 18 -C 22 alkyl group,

  it is preferably a stearyl, arachidyl or behenyl group.

  When R1 represents a C18-C22 alkenyl group, it is

preferably an oleyl group.

  When R 2 represents a substituted ammonium group, it is preferably an ammonium group substituted by one, two or three C 1 -C 4 -alkyl, C- or C 2-4 -alkyl groups, for example a

  mono-, di- or triethanolammonium group.

  When R3 represents a group -S03R2, the two symbols

R2 are preferably identical.

  R2 preferably means an ammonium group.

  R3 preferably means a group SO3R2.

  In each unit (CmH2mO-, m preferably means 2 or 3, more particularly 2. All the units (CmH2mO) being found

  in the molecule are preferably identical.

  The sum n + p is preferably between 18 and 22, and is more particularly equal to 20. The expression "in base form" refers to the central nitrogen atom of the compound of formula I, in non- protonated or

not quaternized.

  The preferred compounds of formula I are those in which R3 is -SO3R2, especially those in which

  R1 represents a stearyl, arachidyl or behenyl group, R2 represents

  an ammonium group, R3 represents a group -SO3NH4, m = 2 and n + p = 20, more particularly a mixture of such compounds in

  which R 1 represents a stearyl, arachidyl and behenyl group.

  Preferred salts of the compounds of formula I are quaternary ammonium salts, for example those which contain

  anion chloride, bromide, methyl sulfate or sulfate.

  According to the invention, to prepare the compounds of formula I, the adduct of 17 to 23 moles per mole of amine is esterified with a C2-C4 alkylene oxide on one or more amines of formula II

R1NH2 II

  in which R 1 is as defined above, with sulfuric acid or one of its functional derivatives and, if desired, converting the compound of formula I, obtained in free acid or base form

  free, in appropriate salt or vice versa.

  The reaction of the C2-C4 alkylene oxide with the amine of

  formula II can be carried out according to the known methods,

  in the presence of a catalyst such as sodium hydroxide

or potassium.

  The mono- or di-esterification of the polyalkoxylated amine with sulfuric acid or one of its functional derivatives can be carried out according to the known methods. Functional derivatives

  Suitable sulfuric acid products include anhydrous, halo-

  genures and amides. The polyalkoxylated amine is preferably mono- or di-esterified by reaction with sulfamic acid, which

  gives directly the compounds of formula I in which R2 represents

  feels an ammonium group. The esterification is advantageously carried out

  at a temperature between 90 and 120 C. It is possible to

  one of the terminal hydroxy groups present in the polyamine amine

  alkoxylated or both, depending on the amount of sulfuric acid or

  its functional derivative used. It is preferably carried out

  in the presence of a solubilising agent, in particular

  urea; such an agent is preferably added in a quantity of

  having 20 to 25% by weight of the final esterified compound.

  When the esterification is complete, it is not necessary to

  remove the urea from the reaction product. Sulphates of formula I

  The resultants are preferably used in admixture with urea.

  The compounds of formula I in which R2 has one of the

  previously given, for example hydrogen, may be

  be transformed according to known methods into compounds of

  corresponding mule I in which R2 has another of the

  fications given previously, for example, other than hydrogen.

  The conversion of the compounds of formula I in base form to the corresponding protonated or quaternized form or the reverse

  can be performed according to known methods. The agents of pro-

  Suitable quaternization and toning agents include hydrochloric acid, hydrobromic acid, dimethyl sulfate,

  Methyl or methyl bromide and benzyl chloride.

- 4-

  The compounds of formula I and their salts can be used

  used as auxiliary products for dyeing or printing

  textile substrates comprising natural or synthetic polyamides

  or a mixture of these polyamides, such as wool, silk or nylon, wool being particularly preferred. The substrate may also consist of a mixture of natural polyamides or

  synthetic fibers with other synthetic fibers such as poly-

  ester. The substrate may be in any conventional form, for example in the form of fibers, filaments,

  yarn, of woven or knitted material, or carpets.

  The subject of the invention is also a method for

  dyeing or printing of textile substrates

  natural or synthetic polyamide fibers, wherein the textile substrate is treated, before or during dyeing or printing, with one or more compounds of formula I, such as

previously defined.

  The compounds of formula I and their salts are advantageously used in an amount representing from 0.2 to 4% by weight, preferably from 0.5 to 3% by weight relative to the weight of the substrate.

to be dyed or printed.

  The method of the invention can be used to dye textile substrates with a dye or a mixture of dyes

  suitable for dyeing natural or synthetic polyamides

  ticks, preferably acidic dyes for wool. The colors

  Suitable acidic woolen materials include various categories

  dyes which may contain at least one sulpho group and optionally

  at least one group capable of reacting with the polyamide fibers. The preferred acid dyes for wool are for example the dyestuffs of triphenylmethane containing at least two sulpho groups, mono- or disazo dyes not metallized.

  containing at least one sulfo group and optionally at least one -

  group likely to react with the fiber, the mono dyes

  azo, disazo, azomethine and metallized formazane, especially copper, chromium, nickel or cobalt complexes, especially those in which a metal atom is -5-

  linked to two molecules of azo dye or to a molecule of

  azo-containing dye and optionally containing at least one sulfo group and optionally at least one group capable of reacting with the fiber, and the anthraquinone dyes containing at least one sulfo group, in particular

  bind those derived from 1-amino-4-arylaminoanthraquinone-2-

  sulphonic acid and 1,4-diarylamino- or 1-cycloalkylamino-4-

  arylaminoanthraquinone-sulfonic acid. Metal complex dyes

  particularly preferred are the disazo dyes

  metal complexes containing two sulfo groups and chromium or cobaltifer 1: 2 complexes whose ligands are

  selected from monoazo, disazo and azomethic dyes

  especially asymmetric chromiferous complexes or

  cobalt 1: 2 azo dyes.

  The groups that can react with the fibers are, for example, halogenated heterocyclic groups such as

  mono-chlorotriazinyl, dichlorotriazinyl, monofluoro-

  azinyl, monofluoropyrimidinyl, difluoropyrimidinyl, fluorine

  chloropyrimidinyl, dichloroquinoxalinyl or methylsulfone-chloro

  methylpyrimidinyl or vinylsulfone. When using a dye containing at least one group capable of reacting with the fiber,

  such a colorant is preferably used in combination with a

  lorant free of group likely to react with the fiber.

  The amount of dye to be used may vary in

  broad limits, depending on the desired dye intensity. Quantities

  appropriate amounts are generally in the range of 0.001 to 10% by weight

relative to the weight of the substrate.

  According to the process of the invention, the substrate to be dyed or printed is treated with the compounds of formula I, in free base or salt form, before or during dyeing or printing. The treatment with the compounds of the invention is suitably carried out in an aqueous acidic medium, preferably at pH values corresponding to the isoelectric point of the natural polyamides, that is to say at pH values included

  between 4 and 5.5, in particular 4.5 and 5. These conditions are

  especially preferred when the substrate to be dyed is wool. The desired pH values can be obtained by adding

  treatment or dyeing bath containing the compounds of

  mule I, a mineral or organic acid such as sulfuric acid,

  phosphoric acid or a lower aliphatic carboxylic acid

  such as formic acid, acetic acid or oxalic acid, and / or

  salt such as ammonium acetate, ammonium sulphate or

sodium tate.

  The application of the compounds of formula I or of their salts

  on the substrate before dyeing or printing, can be carried out

  killed by known methods, for example by exhaustion,

  cladding or printing. They are applied to the substrate preferably

  The bath ratio is variable, and is advantageously in the range of 1: 4 to 4: 1.

  1: 100, preferably between 1: 1 and 1:50.

  After treatment, for example for 20 to 120 minutes, the treatment bath can be discharged and replaced, or used as such for dyeing after cooling and addition of dyes. Dyeing or printing in the presence of the compounds of

  formula I or their salts, may be carried out according to the

  known methods, preferably by exhaustion. The bath ratio, the dyeing temperature and the pH value are preferably as indicated above. The acid or salt, the auxiliary product of formula I and the dye (s) are added to the bath preferably at a temperature between 30 and 70 ° C; the bath is then heated to the desired dyeing temperature and the dyeing is suitably carried out for a period of 20 to 120 minutes, preferably for 30 to 60 minutes. The dyeing completed, the

  Substrate is washed and dried according to conventional methods.

-7-

  Treatment with a compound of the invention or the

  in the presence of a compound of the invention can be carried out by means of conventional dyeing apparatus, for example

  turnstiles, machines for dyeing plastic ribbons

  knots, dyeing machines, beam dyeing machines, vane dyers, jiggers, jet dyeing machines or dyeing machines

the skeins.

  The compounds of formula I and their salts exert a good leveling effect on the substrate. We get intense dyes

  with a high dye yield with improved durability

  friction, without the other solidities, such as

  light and wet fastnesses are affected.

  The compounds of the invention prevent the dichroism of metallurgical complex dyes 1: 2, thus improving the unison of the fiber. They exert a very weak retardation effect, which makes it possible to use 1: 2, acidic and / or reactive metal complex dye mixtures. The compounds of the invention allow

  also clearly improve the rising power of

  rants. When used as auxiliary products for dyeing wool, especially with complex dyes

  metallurgy 1: 2, their effect is such that good results are obtained.

  even in the absence of anionic products having affinity for wool and such as hitherto used in known wool dyeing processes, such as compounds containing at least one linked sulfo group especially on a aromatic ring such as a naphthalenic ring or a benzene ring, for example the reaction products of naphthalenesulfonic acid with formaldehyde, and in the absence of a water-soluble salt of the acid

  tetraboric, for example borax.

74791

- 8-

  In the presence of metal complex dyes 1: 2

  phobes free of sulfo group, the compounds of formula I and their

  salts prevent precipitation, especially of

  such as those resulting from the dehydration of

  additives of dyeing auxiliaries.

  The following examples illustrate the invention without any

  limit its scope. All parts and percentages

  are by weight and temperatures are given in degrees Celsius.

Example 1

  For 6 to 8 hours, 300 g (1 mole) of a commercial fatty amine (weight

  average molecular weight = 300) containing about 48% by weight of stearyl

  amine, 40% by weight of behenylamine and 12% by weight of arachidyl-

  amine, with 880 g (20 moles) of ethylene oxide, in the presence of 3 g of sodium hydroxide. The reaction mixture thus obtained is cooled to 70-75. With stirring, 388 g of urea and then 194 g (2 moles) of amidosulfonic acid are added over 15 minutes in the course of 30 minutes, the reaction mixture being simultaneously heated to 110. After stirring for 6 hours at 110, the esterification is complete. The product obtained can be used as it is or in the form of an aqueous solution.

Example 2

  The procedure is as in Example 1 until the esterification

  cation is completed. The reaction mixture is then cooled to 85 and 126 g of dimethyl sulphate are added dropwise with gentle stirring. The addition is complete, we heat the mixture

  Reaction for another 6 hours at 100. The resulting methyl sulphate

  both can be used as is or as an aqueous solution.

- 9-

Example 3

  10 parts of a woolen fabric are introduced into 400 parts

  water at 40. 0.2 part of the product is added to this bath.

  Binder of formula I prepared in Example 1 and containing about 25% by weight of urea, 0.1 part of CI Acid Red 399 dye and acetic acid in sufficient quantity to adjust the pH value of the dye bath at about 4.8. The whole is boiled in 40 minutes and dyeing is carried out for 60 minutes at the same temperature. After cooling the dye bath, the

  fabric is removed, washed and dried.

  The wool fabric is dyed in a solid red shade pos-

seducing excellent fastness.

  By proceeding in the same manner as in Example 3 but using a mixture of compounds of formula I in which R 1 is as defined above, R 2 is sodium or ethanolammonium, R 3 is hydrogen and n is + p = 17

  or 23, dyes on wool are obtained with a good

  his. Instead of the CI Acid Red 399 dye, it is also possible to use Acid Yellow 21, Acid Yellow 235 CI, Acid Orange 95, Acid Orange 168, Acid Red 263, Acid Blue 113 CI, Acid Blue 269 or Acid Blue 269. CI Acid Blue 334 or a mixture of these dyes; the dyes thus obtained are indicated

by a good unison.

  The compound of formula I used in example 3 can also be replaced by a mixture of compounds of formula Ia

I

R [- N / (CH2CH2O) = - S03NH4 (Ia

R4 (CH2CH2O) _S03NH4

- 10 -

  wherein R1 represents a mixture of alkyl groups containing

  About 48% stearyl, 12% arachidyl and% behenyl, n + p = 20, R4 is methyl and XM is CH3SO3O, with compounds of formula la wherein R4 is benzyl and o D means Ce. When dyeing in the presence of this mixture according to the method used in Example 3, the wool is dyed in one

solid and solid shade.

Example 4

  The procedure is as in Example 3 but using 0.1875 parts of a compound of formula I in which R 1 represents a

  oleyl group, R2 represents a triethanolammonium group, R3 represents

  present hydrogen, m = 3 and n + p = 18, in admixture with 0.0625 parts of urea. We get on the wool a colored dye

  solid red with good solidity.

Example 5

  The procedure is as in Example 3 but uses 10 parts

  nylon 6.6 and 0.3 parts C.I. Acid Blue 269 dye.

  We get a navy blue dye with a very good

  unison and very good solidity.

Example 6

  10 parts of woolen cloth are introduced into 200 parts of water containing 40 parts of 0.3 part of a compound of formula I in

  which R1 represents a mixture of alkyl groups containing

  of 48% stearyl, 12% arachidyl and 40% behenyl, R2 is ammonium, R3 is SO3NH4, m = 4 and n + p = 22, and 0.07 part urea. We rule

  the pH value of the bath to about 4.8 by adding acetic acid

  tick. The mixture is then boiled in 30 minutes and the fabric is boiled for 60 minutes. The bath is discharged and replaced with 400 parts of water at 40 containing 0.15

  part of C.I. Acid Orange dye 168. After having adjusted the

  their pH to 4.8 by addition of acetic acid, we bring everything to

  boiling in 40 minutes and dye the fabric to boiling

  60 minutes. After cooling, the fabric is removed from the bath,

it is washed and dried.

- i1 -

  A dyed fabric is obtained in a united red-orange shade

possessing good solidity.

  In Examples 3 to 6, the auxiliary product of

  mule I used can be replaced by the auxiliary product of formula I of example 2 in corresponding amount, or by a mixture of compounds of formula I in which R 1 represents a mixture of stearyl, behenyl and arachidyl groups as defined above, R2 represents an ammonium group, R3 represents a

  group -S03NH4, m means 2 and n + p = 17 or 23.

-12 -

Claims (16)

  1. The compounds of formula I (CmH2mO) n 503R2 R1 Ns (I) NS (CmH2m0) p -R3 in which Rt represents a C18-C22 alkyl or C18-C22 alkenyl group, R2 represents hydrogen, sodium, potassium, an ammonium group or a substituted ammonium group, R3 represents hydrogen or a group -SO3R2, in each unit (CmH2mO) -, m means 2, 3 or 4, and the sum n + p is between 17 and 23 inclusive,   in base form or in protonated or quaternized form.   2. Compounds according to claim 1, characterized in that   that R1 represents a stearyl, arachidyl or behenyl group.   3. Compounds according to claim 1 or 2, characterized   in that R3 represents a group -SO3R2.   4. Compounds according to any one of claims 1 to   3, characterized in that in each pattern (CmH2mO -), m is 2 or 3.   5. Compounds according to any one of claims 1 to   4, characterized in that the sum n + p is between 18 and 22.   6. Compounds according to any one of claims 1 to   characterized in that R1 represents a stearyl group,   arachidyl or behenyl, R2 represents an ammonium group, R3 represents   has a group -SO3NH4, m = 2 and n + p = 20. - 13 -   7. A process for the preparation of the compounds of formula I   or a mixture of these compounds, characterized in that the adduct of 17 to 23 moles per mole of amine is esterified with a C2-C4 alkylene oxide. on one or more amines of formula II RINH2 (II)   wherein R 1 has the meaning given in claim 1, with sulfuric acid or a functional derivative thereof, and, if desired, converting the compound of formula I, obtained as a free acid or free base, in suitable salt or vice versa.   8.- The use of the specified compounds in any one   Claims 1 to 6 as auxiliary products for the   dyeing or printing of textile substrates comprising   natural or synthetic polyamides.   9.- Method for dyeing or printing substrates   textiles comprising natural or synthetic polyamide fibers   characterized in that the textile substrate is treated before   or during dyeing or printing, by one or more   of formula I as specified in any one of the claims cations 1 to 6.   10. A process according to claim 9, characterized in that the textile substrate is treated with one or more compounds of formula I, wherein R1 represents a stearyl, arachidyl and / or behenyl group, R2 represents an ammonium group,   R 3 represents a group -SO 3 NH 4, m = 2 and n + p = 20.   11. A process according to claim 9 or 10, characterized   in that the compounds of formula I and their salts are used in an amount of from 0.2 to 4% by weight relative to the weight of of the substrate. - 14 -   12. A process according to any one of the claims   9 to 11, characterized in that the textile substrate is dyed or printed.   tile with an acid dye for wool.   13. A process according to claim 12, characterized in that the acid dye for wool comprises at least one sulpho group and optionally at least one group capable of reacting with the fiber.   14. A process according to claim 13, characterized in that the acid dye for wool is chosen from triphenylmethane dyes comprising at least two sulpho groups, unmetallized mono- or disazo dyes containing at least one sulpho group and optionally a sulpho group. group capable of reacting with the fiber, metallized monoazo, disazio, azomethine and formazan dyes possibly containing at least one group that is capable of reacting with the fiber, and / or the dyes   anthraquinone containing at least one sulfo group.   15. A process according to any one of the claims   9 to 14, characterized in that the textile substrate comprises wool. 16. Textile substrates, characterized in that they have been dyed or printed according to the specified method to any one of Claims 9 to 15.